Polymer templated nanowire catalysts

ABSTRACT

Nanowires useful as heterogeneous catalysts are provided. The nanowire catalysts are prepared by polymer templated methods and are useful in a variety of catalytic reactions, for example, the oxidative coupling of methane to ethane and/or ethylene. Related methods for use and manufacture of the same are also disclosed.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application claims the benefit under 35 U.S.C. §119(e) of U.S.Provisional Patent Application No. 61/564,834, filed on Nov. 29, 2011;Provisional Patent Application No. 61/564,836, filed on Nov. 29, 2011;and U.S. Provisional Patent Application No. 61/651,399, filed on May 24,2012; each of which are incorporated herein by reference in theirentireties.

BACKGROUND

1. Technical Field

This invention is generally related to novel nanowire catalysts and,more specifically, to nanowires prepared via polymer templated methods.The nanowires are useful as heterogeneous catalysts in a variety ofcatalytic reactions, such as the oxidative coupling of methane toethylene.

2. Description of the Related Art

Catalysis is the process in which the rate of a chemical reaction iseither increased or decreased by means of a catalyst. Positive catalystsincrease the speed of a chemical reaction, while negative catalysts slowit down. Substances that increase the activity of a catalyst arereferred to as promoters or activators, and substances that deactivate acatalyst are referred to as catalytic poisons or deactivators. Unlikeother reagents, a catalyst is not consumed by the chemical reaction, butinstead participates in multiple chemical transformations. In the caseof positive catalysts, the catalytic reaction generally has a lowerrate-limiting free energy change to the transition state than thecorresponding uncatalyzed reaction, resulting in an increased reactionrate at the same temperature. Thus, at a given temperature, a positivecatalyst tends to increase the yield of desired product while decreasingthe yield of undesired side products. Although catalysts are notconsumed by the reaction itself, they may be inhibited, deactivated ordestroyed by secondary processes, resulting in loss of catalyticactivity.

Catalysts are generally characterized as either heterogeneous orhomogeneous. Heterogeneous catalysts exist in a different phase than thereactants (e.g. a solid metal catalyst and gas phase reactants), and thecatalytic reaction generally occurs on the surface of the heterogeneouscatalyst. Thus, for the catalytic reaction to occur, the reactants mustdiffuse to and/or adsorb onto the catalyst surface. This transport andadsorption of reactants is often the rate limiting step in aheterogeneous catalysis reaction. Heterogeneous catalysts are alsogenerally easily separable from the reaction mixture by commontechniques such as filtration or distillation.

In contrast to a heterogeneous catalyst, a homogenous catalyst exists inthe same phase as the reactants (e.g., a soluble organometallic catalystand solvent-dissolved reactants). Accordingly, reactions catalyzed by ahomogeneous catalyst are controlled by different kinetics than aheterogeneously catalyzed reaction. In addition, homogeneous catalystscan be difficult to separate from the reaction mixture.

While catalysis is involved in any number of technologies, oneparticular area of importance is the petrochemical industry. At thefoundation of the modern petrochemical industry is the energy-intensiveendothermic steam cracking of crude oil. Cracking is used to producenearly all the fundamental chemical intermediates in use today. Theamount of oil used for cracking and the volume of green house gases(GHG) emitted in the process are quite large: cracking consumes nearly10% of the total oil extracted globally and produces 200 M metric tonsof CO₂ equivalent every year (Ren, T, Patel, M. Res. Conserv. Recycl.53:513, 2009). There remains a significant need in this field for newtechnology directed to the conversion of unreactive petrochemicalfeedstocks (e.g. paraffins, methane, ethane, etc.) into reactivechemical intermediates (e.g. olefins), particularly with regard tohighly selective heterogeneous catalysts for the direct oxidation ofhydrocarbons.

While there are multistep paths to convert methane to certain specificchemicals using first; high temperature steam reforming to syngas (amixture of H₂ and CO), followed by stochiometry adjustment andconversion to either methanol or, via the Fischer-Tropsch (F-T)synthesis, to liquid hydrocarbon fuels such as diesel or gasoline, thisdoes not allow for the formation of certain high value chemicalintermediates. This multi-step indirect method also requires a largecapital investment in facilities and is expensive to operate, in partdue to the energy intensive endothermic reforming step. (For instance,in methane reforming, nearly 40% of methane is consumed as fuel for thereaction.) It is also inefficient in that a substantial part of thecarbon fed into the process ends up as the GHG CO₂, both directly fromthe reaction and indirectly by burning fossil fuels to heat thereaction. Thus, to better exploit the natural gas resource, directmethods that are more efficient, economical and environmentallyresponsible are required.

One of the reactions for direct natural gas activation and itsconversion into a useful high value chemical, is the oxidative couplingof methane (“OCM”) to ethylene: 2CH₄+O₂→C₂H₄+2H₂O. See, e.g., Zhang, Q.,Journal of Natural Gas Chem., 12:81, 2003; Olah, G. “HydrocarbonChemistry”, Ed. 2, John Wiley & Sons (2003). This reaction is exothermic(ΔH=−67 kcals/mole) and has typically been shown to occur at very hightemperatures (>700° C.). Although the detailed reaction mechanism is notfully characterized, experimental evidence suggests that free radicalchemistry is involved. (Lunsford, J. Chem. Soc., Chem. Comm., 1991; H.Lunsford, Angew. Chem., Int. Ed. Engl., 34:970, 1995). In the reaction,methane (CH₄) is activated on the catalyst surface, forming methylradicals which then couple in the gas phase to form ethane (C₂H₆),followed by dehydrogenation to ethylene (C₂H₄). Several catalysts haveshown activity for OCM, including various forms of iron oxide, V₂O₅,MoO₃, Co₃O₄, Pt—Rh, Li/ZrO₂, Ag—Au, Au/Co₃O₄, Co/Mn, CeO₂, MgO, La₂O₃,Mn₃O₄, Na₂WO₄, MnO, ZnO, and combinations thereof, on various supports.A number of doping elements have also proven to be useful in combinationwith the above catalysts.

Since the OCM reaction was first reported over thirty years ago, it hasbeen the target of intense scientific and commercial interest, but thefundamental limitations of the conventional approach to C—H bondactivation appear to limit the yield of this attractive reaction.Specifically, numerous publications from industrial and academic labshave consistently demonstrated characteristic performance of highselectivity at low conversion of methane, or low selectivity at highconversion (J. A. Labinger, Cat. Lett., 1:371, 1988). Limited by thisconversion/selectivity threshold, no OCM catalyst has been able toexceed 20-25% combined C₂ yield (i.e. ethane and ethylene), and moreimportantly, all such reported yields operate at extremely hightemperatures (>800 C).

In this regard, it is believed that the low yield of desired products(i.e. C₂H₄ and C₂H₆) is caused by the unique homogeneous/heterogeneousnature of the reaction. Specifically, due to the high reactiontemperature, a majority of methyl radicals escape the catalyst surfaceand enter the gas phase. There, in the presence of oxygen and hydrogen,multiple side reactions are known to take place (J. A. Labinger, Cat.Lett., 1:371, 1988). The non-selective over-oxidation of hydrocarbons toCO and CO₂ (e.g., complete oxidation) is the principal competing fastside reaction. Other undesirable products (e.g. methanol, formaldehyde)have also been observed and rapidly react to form CO and CO₂.

In order to result in a commercially viable OCM process, a catalystoptimized for the activation of the C—H bond of methane at lowertemperatures (e.g. 500-700° C.), higher activities and higher pressuresare required. While the above discussion has focused on the OCMreaction, numerous other catalytic reactions (as discussed in greaterdetail below) would significantly benefit from catalytic optimization.

One type of catalyst expected to meet the above need are nanowirecatalysts comprising various metal elements; however, methods forpreparation of nanowire catalysts which fulfill these needs are notreadily available in the art. Accordingly, there remains a need in theart for improved catalysts and, more specifically, a need for novelapproaches to catalyst preparation and design for improving the yieldof, for example, the OCM reaction and other catalyzed reactions. Thepresent invention fulfills these needs and provides further relatedadvantages.

BRIEF SUMMARY

As noted above, the present disclosure is directed to nanowires, inparticular nanowires prepared via polymer template methods. Thenanowires find utility as catalysts in any number of chemical reactions,for example in the oxidative coupling of methane. In one embodiment thedisclosure provides a method for preparing a nanowire comprising a metaloxide, a metal oxy-hydroxide, a metal oxycarbonate or a metal carbonate,the method comprising:

a) providing a solution comprising a plurality of polymer templates;

(b) introducing at least one metal ion and at least one anion to thesolution under conditions and for a time sufficient to allow fornucleation and growth of a nanowire comprising a plurality of metalsalts (M_(m)X_(n)Z_(p)) on the template; and

(c) optionally converting the nanowire (M_(m)X_(n)Z_(p)) to a metaloxide nanowire comprising a plurality of metal oxides (M_(x)O_(y)),metal oxy-hydroxides (M_(x)O_(y)OH_(z)), metal oxycarbonates(M_(x)O_(y)(CO₃)_(z)), metal carbonate (M_(x)(CO₃)_(y)) or combinationsthereof

wherein:

M is, at each occurrence, independently a metal element from any ofGroups 1 through 7, lanthanides or actinides;

X is, at each occurrence, independently hydroxides, carbonates,bicarbonates, phosphates, hydrogenphosphates, dihydrogenphosphates,sulfates, nitrates or oxalates;

Z is O;

n, m, x and y are each independently a number from 1 to 100; and

p is a number from 0 to 100.

In certain embodiments of the foregoing method, the polymer templatecomprises PVP (polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI(polyethyleneimine), PEG (polyethyleneglycol), polyethers, polyesters,polyamides, dextran, sugar polymers, functionalized hydrocarbonpolymers, functionalized polystyrene, polylactic acid, polycaprolactone,polyglycolic acid, poly(ethylene glycol)-poly(propyleneglycol)-poly(ethylene glycol) or copolymers or combinations thereof. Forexample, in some embodiments the polymer template is functionalized withat least one of amine, carboxylic acid, sulfate, alcohol, halogen orthiol groups, and in other embodiments the polymer template comprises ahydrocarbon polymer or a polystyrene polymer functionalized with atleast one of amine, carboxylic acid, sulfate, alcohol, halogen or thiolgroups.

In other embodiments, the method further comprises freeze drying thenanowire, and in some embodiments the solution comprising the polymertemplate is in the form of a gel, for example, some embodiments comprisea step of base treatment, for example base treatment of a gel, andprecipitating at least one metal.

In other embodiments of the foregoing method, the method furthercomprises use of two or more different metal ions.

In another aspect, the present disclosure is directed to a method forpreparing a nanowire comprising a metal oxide, a metal oxy-hydroxide, ametal oxycarbonate or a metal carbonate, the method comprises:

a) providing a solution comprising a plurality of a multifunctionalcoordinating ligands;

(b) introducing at least one metal ion to the solution, thereby forminga metal ion-ligand complex; and

(c) introducing a polyalcohol to the solution, wherein the polyalcoholpolymerizes with the metal-ion ligand complex to form a polymerizedmetal ion-ligand complex.

In some embodiments, the multifunctional coordinating ligand is analpha-hydroxycarboxylic acid. For example, in some embodiments themultifunctional coordinating ligand is citric acid.

In other embodiments, the polyalcohol is ethylene glycol or glycerol.

In some embodiments, the foregoing method comprises heating thepolymerized metal ion-ligand complex to remove substantially all organicmaterial, while in other embodiments, the method further comprisesheating the polymerized metal ion-ligand complex to obtain a metaloxide.

In another embodiment, the disclosure provides a method for preparingmetal oxide, metal oxy-hydroxide, metal oxycarbonate or metal carbonatecatalytic nanowires in a core/shell structure, the method comprising:

(a) providing a solution that includes a plurality of polymer templates;

(b) introducing a first metal ion and a first anion to the solutionunder conditions and for a time sufficient to allow for nucleation andgrowth of a first nanowire (M1_(m1)X1_(n1)Z_(p1)) on the template; and

(c) introducing a second metal ion and optionally a second anion to thesolution under conditions and for a time sufficient to allow fornucleation and growth of a second nanowire (M2_(m2)X2_(n2)Z_(p2)) on thefirst nanowire (M1_(m1)X1_(n1)Z_(p1));

(d) converting the first nanowire (M1_(m1)X1_(n1)Z_(p1)) and the secondnanowire (M2_(m2)X2_(n2)Z_(p2)) to the respective metal oxide nanowires(M1_(x1)O_(y1)) and (M2_(x2)O_(y2)), the respective metal oxy-hydroxidenanowires (M1_(x1)O_(y1)OH_(z1)) and (M2_(x2)O_(y2)OH_(z2)) therespective metal oxycarbonate nanowires (M1_(x1)O_(y1)(CO₃)_(z1)) and(M2_(x2)O_(y2)(CO₃)_(z2)) or the respective metal carbonate nanowires(M1_(x1)(CO₃)_(y1)) and (M2_(x2)(CO₃)_(y2)),

wherein:

M1 and M2 are the same or different and independently selected from ametal element;

X1 and X2 are the same or different and independently hydroxides,carbonates, bicarbonates, phosphates, hydrogenphosphates,dihydrogenphosphates, sulfates, nitrates or oxalates;

Z is O;

n1, m1n2, m2, x1, y1, z1, x2, y2 and z2 are each independently a numberfrom 1 to 100; and

p1 and p2 are independently a number from 0 to 100.

In certain embodiments of the foregoing, the polymer template comprisesPVP (polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI(polyethyleneimine), PEG (polyethyleneglycol), polyethers, polyesters,polyamides, dextran, sugar polymers, functionalized hydrocarbonpolymers, functionalized polystyrene, polylactic acid, polycaprolactone,polyglycolic acid, poly(ethylene glycol)-poly(propyleneglycol)-poly(ethylene glycol) or copolymers or combinations thereof. Forexample, in some embodiments the polymer template is functionalized withat least one of amine, carboxylic acid, sulfate, alcohol, halogen orthiol groups, and in other embodiments the polymer template comprises ahydrocarbon polymer or a polystyrene polymer functionalized with atleast one of amine, carboxylic acid, sulfate, alcohol, halogen or thiolgroups. In other embodiments, M1 and M2 are different.

In still other embodiments, the disclosure provides a method forpreparing a catalytic nanowire, the method comprising:

admixing (A) with a mixture comprising (B) and (C);

admixing (B) with a mixture comprising (A) and (C); or

admixing (C) with a mixture comprising (A) and (B) to obtain a mixturecomprising (A), (B) and (C), wherein (A), (B), and (C) comprise,respectively:

(A) a polymer template;

(B) one or more salts comprising one or more elements selected fromGroups 1 through 7, lanthanides and actinides and hydrates thereof; and

(C) one or more anion precursors.

In certain embodiments of the foregoing, the mixture comprising (B) and(C) has been prepared by admixing (B) and (C), the mixture comprising(A) and (C) has been prepared by admixing (A) and (C) or the mixturecomprising (A) and (B) has been prepared by admixing (A) and (B).

In other embodiments, the one or more salts comprise chlorides,bromides, iodides, nitrates, sulfates, acetates, oxides, oxalates,oxyhalides, oxynitrates, phosphates, hydrogenphosphate,dihydrogenphosphate or mixtures thereof. For example, the one or moresalts comprise MgCl₂, LaCl₃, ZrCl₄, WCl₄, MoCl₄, MnCl₂MnCl₃, Mg(NO₃)₂,La(NO₃)₃, ZrOCl₂, Mn(NO₃)₂, Mn(NO₃)₃, ZrO(NO₃)₂, Zr(NO₃)₄ or mixturesthereof. In other embodiments, the one or more salts comprise Mg, Ca,Mg, W, La, Nd, Sm, Eu, W, Mn, Zr or mixtures thereof.

In some embodiments, the one or more anion precursors comprises alkalimetal hydroxides, alkaline earth metal hydroxides, carbonates,bicarbonates, ammonium hydroxides, or mixtures thereof. For example, insome embodiments the one or more anion precursors comprises LiOH, NaOH,KOH, Sr(OH)₂, Ba(OH)₂, Na₂CO₃, K₂CO₃, NaHCO₃, KHCO₃, and NR₄OH, whereinR is selected from H, and C₁-C₆ alkyl.

In certain other embodiments of the above method, the polymer templatecomprises PVP (polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI(polyethyleneimine), PEG (polyethyleneglycol), polyethers, polyesters,polyamides, dextran, sugar polymers, functionalized hydrocarbonpolymers, functionalized polystyrene, polylactic acid, polycaprolactone,polyglycolic acid, poly(ethylene glycol)-poly(propyleneglycol)-poly(ethylene glycol) or copolymers or combinations thereof. Forexample, in some embodiments the polymer template is functionalized withat least one of amine, carboxylic acid, sulfate, alcohol, halogen orthiol groups, and in other embodiments the polymer template comprises ahydrocarbon polymer or a polystyrene polymer functionalized with atleast one of amine, carboxylic acid, sulfate, alcohol, halogen or thiolgroups.

In other embodiments, the method further comprises allowing the mixturecomprising (A), (B), and (C) to stand at a temperature of from about 4°C. to about 80° C. for a period of time sufficient to allow nucleationof the catalytic nanowires, and other examples further comprise adding adoping element comprising metal elements, semi-metal elements, non-metalelements or combinations thereof to the mixture comprising (A), (B), and(C).

Some embodiments comprise calcining the nanowires, for example in someembodiments calcining the nanowires comprises heating the nanowires at450° C. or greater for at least 60 min.

In other embodiments, the method further comprises doping the nanowires,wherein doping the nanowires comprises contacting the nanowires with asolution comprising a dopant and evaporating any excess liquid, whereinthe dopant comprises a metal element, a semi-metal element, a non-metalelement or combinations thereof.

In another embodiment, the disclosure provides a method for preparingmetal oxide nanowires, the method comprising:

(a) providing a solution comprising a plurality of polymer templates;and

(b) introducing a compound comprising a metal to the solution underconditions and for a time sufficient to allow for nucleation and growthof a nanowire (M_(m)Y_(n)) on the template;

wherein:

M is a metal element from any of Groups 1 through 7, lanthanides oractinides;

Y is O,

n and m are each independently a number from 1 to 100.

In some embodiments of the foregoing, the polymer template comprises PVP(polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI (polyethyleneimine),PEG (polyethyleneglycol), polyethers, polyesters, polyamides, dextran,sugar polymers, functionalized hydrocarbon polymers, functionalizedpolystyrene, polylactic acid, polycaprolactone, polyglycolic acid,poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) orcopolymers or combinations thereof. For example, in some embodiments thepolymer template is functionalized with at least one of amine,carboxylic acid, sulfate, alcohol, halogen or thiol groups, and in otherembodiments the polymer template comprises a hydrocarbon polymer or apolystyrene polymer functionalized with at least one of amine,carboxylic acid, sulfate, alcohol, halogen or thiol groups.

The present disclosure also provides a nanowire prepared according toany of the foregoing methods and in other embodiments provides acatalytic material comprising the same.

Other embodiments provide a method for the preparation of a downstreamproduct of ethylene, the method comprising converting methane intoethylene in the presence of a nanowire prepared according to any of theforegoing methods or a catalytic material comprising the same, andfurther oligomerizing the ethylene to prepare a downstream product ofethylene.

In another embodiment, a process for the preparation of ethylene frommethane comprising contacting a mixture comprising oxygen and methane ata temperature below 900° C. with a nanowire prepared according to any ofthe foregoing methods or a catalytic material comprising the same isprovided.

These and other aspects of the invention will be apparent upon referenceto the following detailed description. To this end, various referencesare set forth herein which describe in more detail certain backgroundinformation, procedures, compounds and/or compositions, and are eachhereby incorporated by reference in their entirety.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

In the drawings, the sizes and relative positions of elements in thedrawings are not necessarily drawn to scale. For example, the variouselements and angles are not drawn to scale, and some of these elementsare arbitrarily enlarged and positioned to improve drawing legibility.Further, the particular shapes of the elements as drawn are not intendedto convey any information regarding the actual shape of the particularelements, and have been selected solely for ease of recognition in thedrawings.

FIG. 1 schematically depicts a first part of an OCM reaction at thesurface of a metal oxide catalyst.

FIG. 2 shows a high throughput work flow for synthetically generatingand testing libraries of nanowires.

FIG. 3 illustrates a nanowire in one embodiment.

FIG. 4 illustrates a nanowire in a different embodiment.

FIG. 5 illustrates a plurality of nanowires.

FIG. 6 is a flow chart of an exemplary nucleation process for forming ametal oxide nanowire.

FIG. 7 is a flow chart of an exemplary sequential nucleation process forforming a nanowire in a core/shell configuration.

FIG. 8 schematically depicts a carbon dioxide reforming reaction on acatalytic surface.

FIG. 9 is a flow chart for data collection and processing in evaluatingcatalytic performance.

FIG. 10 illustrates a number of downstream products of ethylene.

FIG. 11 depicts a representative process for preparing a lithium dopedMgO nanowire.

FIG. 12 depicts OCM and ethylene oligomerization modules.

DETAILED DESCRIPTION OF THE INVENTION

In the following description, certain specific details are set forth inorder to provide a thorough understanding of various embodiments.However, one skilled in the art will understand that the invention maybe practiced without these details. In other instances, well-knownstructures have not been shown or described in detail to avoidunnecessarily obscuring descriptions of the embodiments. Unless thecontext requires otherwise, throughout the specification and claimswhich follow, the word “comprise” and variations thereof, such as,“comprises” and “comprising” are to be construed in an open, inclusivesense, that is, as “including, but not limited to.” Further, headingsprovided herein are for convenience only and do not interpret the scopeor meaning of the claimed invention.

Reference throughout this specification to “one embodiment” or “anembodiment” means that a particular feature, structure or characteristicdescribed in connection with the embodiment is included in at least oneembodiment. Thus, the appearances of the phrases “in one embodiment” or“in an embodiment” in various places throughout this specification arenot necessarily all referring to the same embodiment. Furthermore, theparticular features, structures, or characteristics may be combined inany suitable manner in one or more embodiments. Also, as used in thisspecification and the appended claims, the singular forms “a,” “an,” and“the” include plural referents unless the content clearly dictatesotherwise. It should also be noted that the term “or” is generallyemployed in its sense including “and/or” unless the content clearlydictates otherwise.

As discussed above, heterogeneous catalysis takes place between severalphases. Generally, the catalyst is a solid, the reactants are gases orliquids and the products are gases or liquids. Thus, a heterogeneouscatalyst provides a surface that has multiple active sites foradsorption of one more gas or liquid reactants. Once adsorbed, certainbonds within the reactant molecules are weakened and dissociate,creating reactive fragments of the reactants, e.g., in free radicalforms. One or more products are generated as new bonds between theresulting reactive fragments form, in part, due to their proximity toeach other on the catalytic surface.

As an example, FIG. 1 shows schematically the first part of an OCMreaction that takes place on the surface of a metal oxide catalyst 10which is followed by methyl radical coupling in the gas phase. A crystallattice structure of metal atoms 14 and oxygen atoms 20 are shown, withan optional dopant 24 incorporated into the lattice structure. In thisreaction, a methane molecule 28 comes into contact with an active site(e.g., surface oxygen 30) and becomes activated when a hydrogen atom 34dissociates from the methane molecule 28. As a result, a methyl radical40 is generated on or near the catalytic surface. Two methyl radicalsthus generated can couple in the gas phase to create ethane and/orethylene, which are collectively referred to as the “C2” couplingproducts.

It is generally recognized that the catalytic properties of a catalyststrongly correlate to its surface morphology. Typically, the surfacemorphology can be defined by geometric parameters such as: (1) thenumber of surface atoms (e.g., the surface oxygen of FIG. 1) thatcoordinate to the reactant; and (2) the degree of coordinativeunsaturation of the surface atoms, which is the coordination number ofthe surface atoms with their neighboring atoms. For example, thereactivity of a surface atom decreases with decreasing coordinativeunsaturation. For example, for the dense surfaces of a face-centeredcrystal, a surface atom with 9 surface atom neighbors will have adifferent reactivity than one with 8 neighbors. Additional surfacecharacteristics that may contribute to the catalytic properties include,for example, crystal dimensions, lattice distortion, surfacereconstructions, defects, grain boundaries, and the like. See, e.g., VanSanten R. A. et al New Trends in Materials Chemistry 345-363 (1997).

Catalysts in nano-size dimensions have substantially increased surfaceareas compared to their counterpart bulk materials. The catalyticproperties are expected to be enhanced as more surface active sites areexposed to the reactants. Typically in traditional preparations, atop-down approach (e.g., milling) is adopted to reduce the size of thebulk material. However, the surface morphologies of such catalystsremain largely the same as those of the parent bulk material.

Various embodiments described herein are directed to nanowires withcontrollable or tunable surface morphologies. In particular, nanowiressynthesized by a “bottom up” approach, by which inorganicpolycrystalline nanowires are nucleated from solution phase in thepresence of a template, e.g., a polymer template. By varying thesynthetic conditions, nanowires having different compositions and/ordifferent surface morphologies are generated.

In contrast to a bulk catalyst of a given elemental composition, whichis likely to have a particular corresponding surface morphology, diversenanowires with different surface morphologies can be generated despitehaving the same elemental composition. In this way, morphologicallydiverse nanowires can be created and screened according to theircatalytic activity and performance parameters in any given catalyticreaction. Advantageously, the nanowires disclosed herein and methods ofproducing the same have general applicability to a wide variety ofheterogeneous catalyses, including without limitation: oxidativecoupling of methane (e.g., FIG. 1), oxidative dehydrogenation of alkanesto their corresponding alkenes, selective oxidation of alkanes toalkenes and alkynes, oxidation of carbon monoxide, dry reforming ofmethane, selective oxidation of aromatics, Fischer-Tropsch reaction,hydrocarbon cracking and the like.

FIG. 2 schematically shows a high throughput work flow for syntheticallygenerating libraries of morphologically or compositionally diversenanowires and screening for their catalytic properties. An initial phaseof the work flow involves a primary screening, which is designed tobroadly and efficiently screen a large and diverse set of nanowires thatlogically could perform the desired catalytic transformation. Forexample, certain doped bulk metal oxides (e.g., Li/MgO and Sr/La₂O₃) areknown catalysts for the OCM reaction. Therefore, nanowires of variousmetal oxide compositions and/or surface morphologies can be prepared andevaluated for their catalytic performances in an OCM reaction.

More specifically, the work flow 100 begins with designing syntheticexperiments based on solution phase template formations (block 110). Thesynthesis, subsequent treatments and screenings can be manual orautomated. As will be discussed in more detail herein, by varying thesynthetic conditions, nanowires can be prepared with various surfacemorphologies and/or compositions in respective microwells (block 114).The nanowires are subsequently calcined and then optionally doped (block120). Optionally, the doped and calcined nanowires are further mixedwith a catalyst support (block 122). Beyond the optional support step,all subsequent steps are carried out in a “wafer” format, in whichnanowire catalysts are deposited in a quartz wafer that has been etchedto create an ordered array of microwells. Each microwell is aself-contained reactor, in which independently variable processingconditions can be designed to include, without limitation, respectivechoices of elemental compositions, catalyst support, reactionprecursors, templates, reaction durations, pH values, temperatures,ratio between reactants, gas flows, and calcining conditions (block124). Due to design constraints of some wafers, in some embodimentscalcining and other temperature variables are identical in allmicrowells. A wafer map 130 can be created to correlate the processingconditions to the nanowire in each microwell. A library of diversenanowires can be generated in which each library member corresponds to aparticular set of processing conditions and corresponding compositionaland/or morphological characteristics.

Nanowires obtained under various synthetic conditions are thereafterdeposited in respective microwells of a wafer (140) for evaluating theirrespective catalytic properties in a given reaction (blocks 132 and134). The catalytic performance of each library member can be screenedserially by several known primary screening technologies, includingscanning mass spectroscopy (SMS) (Symyx Technologies Inc., Santa Clara,Calif.). The screening process is fully automated, and the SMS tool candetermine if a nanowire is catalytically active or not, as well as itsrelative strength as a catalyst at a particular temperature. Typically,the wafer is placed on a motion control stage capable of positioning asingle well below a probe that flows the feed of the starting materialover the nanowire surface and removes reaction products to a massspectrometer and/or other detector technologies (blocks 134 and 140).The individual nanowire is heated to a preset reaction temperature,e.g., using a CO₂ IR laser from the backside of the quartz wafer and anIR camera to monitor temperature and a preset mixture of reactant gases.The SMS tool collects data with regard to the consumption of thereactant(s) and the generation of the product(s) of the catalyticreaction in each well (block 144), and at each temperature and flowrate.

The SMS data obtained as described above provide information on relativecatalytic properties among all the library members (block 150). In orderto obtain more quantitative data on the catalytic properties of thenanowires, possible hits that meet certain criteria are subjected to asecondary screening (block 154). Typically, secondary screeningtechnologies include a single, or alternatively multiple channelfixed-bed or fluidized bed reactors (as described in more detailherein). In parallel reactor systems or multi-channel fixed-bed reactorsystem, a single feed system supplies reactants to a set of flowrestrictors. The flow restrictors divide the flows evenly among parallelreactors. Care is taken to achieve uniform reaction temperature betweenthe reactors such that the various nanowires can be differentiatedsolely based on their catalytic performances. The secondary screeningallows for accurate determination of catalytic properties such asselectivity, yield and conversion. (block 160). These results serve as afeedback for designing further nanowire libraries. Additionaldescription of SMS tools in a combinatorial approach for discoveringcatalysts can be found in, e.g., Bergh, S. et al. Topics in Catalysts23:1-4, 2003.

Thus, in accordance with various embodiments described herein,compositional and morphologically diverse nanowires can be rationallysynthesized to meet catalytic performance criteria. These and otheraspects of the present disclosure are described in more detail below.

DEFINITIONS

As used herein, and unless the context dictates otherwise, the followingterms have the meanings as specified below.

“Catalyst” means a substance that alters the rate of a chemicalreaction. A catalyst may either increase the chemical reaction rate(i.e. a “positive catalyst”) or decrease the reaction rate (i.e. a“negative catalyst”). Catalysts participate in a reaction in a cyclicfashion such that the catalyst is cyclically regenerated. “Catalytic”means having the properties of a catalyst.

“Polymer” refers to a molecule comprised of two or more repeatingstructural units (i.e., “monomers”). The structural units are typicallyconnected by covalent bonds. The structural units are, at eachoccurrence, independently the same or different and can be connected inany order (e.g., random, repeating, block copolymer, etc.). An exemplarypolymer is polyethylene, which can be prepared using a process employingthe disclosed nanowires. Certain embodiments of the polymers describedherein are suitable for use as a template for forming the disclosednanowires. Polymers in this respect include, but are not limited to, PVP(polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI (polyethyleneimine),PEG (polyethyleneglycol), polyethers, polyesters, polyamides, dextran,sugar polymers, functionalized hydrocarbon polymers, functionalizedpolystyrene, polylactic acid, polycaprolactone, polyglycolic acid,poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol),copolymers and combinations of the foregoing and the like.

“Functionalized” when used in reference to a polymer means the polymermay be substituted with one or more functional groups. In general, thefunctional groups are moieties capable of interaction with metal ions(e.g., via coordination or other interaction) and are useful forinitiating nucleation of the nanowires. Representative functional groupsinclude, but are not limited to, amine, carboxylic acid, sulfate,alcohol, halogen (e.g., F, Cl, Br or I) and/or thiol moieties. Unlessspecifically stated otherwise, the polymers described herein areoptionally functionalized (i.e., may either be unfunctionalized orfunctionalized with one or more functional groups).

“Nanoparticle” means a particle having at least one diameter on theorder of nanometers (e.g. between about 1 and 100 nanometers).

“Nanowire” means a nanowire structure having at least one diameter onthe order of nanometers (e.g. between about 1 and 100 nanometers) and anaspect ratio greater than 10:1. The “aspect ratio” of a nanowire is theratio of the actual length (L) of the nanowire to the diameter (D) ofthe nanowire. Aspect ratio is expressed as L:D.

“Polycrystalline nanowire” means a nanowire having multiple crystaldomains. Polycrystalline nanowires generally have different morphologies(e.g. bent vs. straight) as compared to the corresponding“single-crystalline” nanowires.

“Effective length” of a nanowire means the shortest distance between thetwo distal ends of a nanowire as measured by transmission electronmicroscopy (TEM) in bright field mode at 5 keV. “Average effectivelength” refers to the average of the effective lengths of individualnanowires within a plurality of nanowires.

“Actual length” of a nanowire means the distance between the two distalends of a nanowire as traced through the backbone of the nanowire asmeasured by TEM in bright field mode at 5 keV. “Average actual length”refers to the average of the actual lengths of individual nanowireswithin a plurality of nanowires.

The “diameter” of a nanowire is measured in an axis perpendicular to theaxis of the nanowire's actual length (i.e. perpendicular to thenanowires backbone). The diameter of a nanowire will vary from narrow towide as measured at different points along the nanowire backbone. Asused herein, the diameter of a nanowire is the most prevalent (i.e. themode) diameter.

The “ratio of effective length to actual length” is determined bydividing the effective length by the actual length. A nanowire having a“bent morphology” will have a ratio of effective length to actual lengthof less than one as described in more detail herein. A straight nanowirewill have a ratio of effective length to actual length equal to one asdescribed in more detail herein.

“Inorganic” means a substance comprising a metal element. Typically, aninorganic can be one or more metals in its elemental state, or morepreferably, a compound formed by a metal ion (M^(n+), wherein n 1, 2, 3,4, 5, 6 or 7) and an anion (X^(m−), m is 1, 2, 3 or 4), which balanceand neutralize the positive charges of the metal ion throughelectrostatic interactions. Non-limiting examples of inorganic compoundsinclude oxides, hydroxides, halides, nitrates, sulfates, carbonates,phosphates, acetates, oxalates, and combinations thereof, of metalelements. Other non-limiting examples of inorganic compounds includeLi₂CO₃, Li₂PO₄, LiOH, Li₂O, LiCl, LiBr, LiL, Li₂C₂O₄, Li₂SO₄, Na₂CO₃,Na₂PO₄, NaOH, Na₂O, NaCl, NaBr, NaI, Na₂C₂O₄, Na₂SO₄, K₂CO₃, K₂PO₄, KOH,K₂O, KCl, KBr, KI, K₂C₂O₄, K₂SO₄, Cs₂CO₃, CsPO₄, CsOH, Cs₂O, CsCl, CsBr,CsI, CsC₂O₄, CsSO₄, Be(OH)₂, BeCO₃, BePO₄, BeO, BeCl₂, BeBr₂, BeI₂,BeC₂O₄. BeSO₄, Mg(OH)₂, MgCO₃, MgPO₄, MgO, MgCl₂, MgBr₂, MgI₂, MgC₂O₄.MgSO₄, Ca(OH)₂, CaO, CaCO₃, CaPO₄, CaCl₂, CaBr₂, CaI₂, Ca(OH)₂, CaC₂O₄,CaSO₄, Y₂O₃, Y₂(CO₃)₃, Y₂(PO₄)₃, Y(OH)₃, YCl₃, YBr₃, YI₃, Y₂(C₂O4)₃,Y₂(SO4)₃, Zr(OH)₄, Zr(CO₃)₂, Zr(PO₄)₂, ZrO(OH)₂, ZrO2, ZrCl₄, ZrBr₄,ZrI₄, Zr(C₂O₄)₂, Zr(SO₄)₂, Ti(OH)₄, TiO(OH)₂, Ti(CO₃)₂, Ti(PO₄)₂, TiO2,TiCl₄, TiBr₄, TiI₄, Ti(C₂O₄)₂, Ti(SO₄)₂, BaO, Ba(OH)₂, BaCO₃, BaPO₄,BaCl₂, BaBr₂, BaI₂, BaC₂O₄, BaSO₄, La(OH)₃, La₂(CO₃)₃, La₂(PO₄)₃, La₂O₃,LaCl₃, LaBr₃, LaI₃, La₂(C₂O₄)₃, La₂(SO₄)₃, Ce(OH)₄, Ce(CO₃)₂, Ce(PO₄)₂,CeO₂, Ce₂O₃, CeCl₄, CeBr₄, CeI₄, Ce(C₂O₄)₂, Ce(SO₄)₂, ThO₂, Th(CO₃)₂,Th(PO₄)₂, ThCl₄, ThBr₄, ThI₄, Th(OH)₄, Th(C₂O₄)₂, Th(SO₄)₂, Sr(OH)₂,SrCO₃, SrPO₄, SrO, SrCl₂, SrBr₂, SrI₂, SrC₂O₄, SrSO₄, Sm₂O₃, Sm₂(CO₃)₃,Sm₂(PO₄)₃, SmCl₃, SmBr₃, SmI₃, Sm(OH)₃, Sm₂(CO3)₃, Sm₂(C₂O₃)₃,Sm₂(SO₄)₃, LiCa₂Bi₃O₄Cl₆, Na₂WO₄, K/SrCoO₃, K/Na/SrCoO₃, Li/SrCoO₃,SrCoO₃, molybdenum oxides, molybdenum hydroxides, molybdenum carbonates,molybdenum phosphates, molybdenum chlorides, molybdenum bromides,molybdenum iodides, molybdenum oxalates, molybdenum sulfates, manganeseoxides, manganese chlorides, manganese bromides, manganese iodides,manganese hydroxides, manganese oxalates, manganese sulfates, manganesetugstates, vanadium oxides, vanadium carbonates, vanadium phosphates,vanadium chlorides, vanadium bromides, vanadium iodides, vanadiumhydroxides, vanadium oxalates, vanadium sulfates, tungsten oxides,tungsten carbonates, tungsten phosphates, tungsten chlorides, tungstenbromides, tungsten iodides, tungsten hydroxides, tungsten oxalates,tungsten sulfates, neodymium oxides, neodymium carbonates, neodymiumphosphates, neodymium chlorides, neodymium bromides, neodymium iodides,neodymium hydroxides, neodymium oxalates, neodymium sulfates, europiumoxides, europium carbonates, europium phosphates, europium chlorides,europium bromides, europium iodides, europium hydroxides, europiumoxalates, europium sulfates rhenium oxides, rhenium carbonates, rheniumphosphates, rhenium chlorides, rhenium bromides, rhenium iodides,rhenium hydroxides, rhenium oxalates, rhenium sulfates, chromium oxides,chromium carbonates, chromium phosphates, chromium chlorides, chromiumbromides, chromium iodides, chromium hydroxides, chromium oxalates,chromium sulfates, potassium molybdenum oxides and the like.

“Salt” means a compound comprising negative and positive ions. Salts aregenerally comprised of cations and counter ions. Under appropriateconditions, e.g., the solution also comprises a template, the metal ion(M^(n+)) and the anion (X^(m−)) bind to the template to inducenucleation and growth of a nanowire of M_(m)X_(n) on the template.“Anion precursor” thus is a compound that comprises an anion and acationic counter ion, which allows the anion (X^(m−)) dissociate fromthe cationic counter ion in a solution. Specific examples of the metalsalt and anion precursors are described in further detail herein.

“Oxide” refers to a metal compound comprising oxygen. Examples of oxidesinclude, but are not limited to, metal oxides (M_(x)O_(y)), metaloxyhalides (M_(x)O_(y)X_(z)), metal oxynitrates (M_(x)O_(y)(NO₃)_(z)),metal phosphates (M_(x)(PO₄)_(y)), metal oxycarbonates(M_(x)O_(y)(CO₃)_(z)), metal carbonates, metal oxyhydroxides(M_(x)O_(y)(OH)_(z)) and the like, wherein x, y and z are numbers from 1to 100.

“Crystal domain” means a continuous region over which a substance iscrystalline.

“Single-crystalline nanowires” means a nanowire having a single crystaldomain.

“Template” is any synthetic and/or natural material that provides atleast one nucleation site where ions can nucleate and grow to formnanoparticles. In certain embodiments, the templates comprise polymers.Typically, the polymer comprises multiple binding sites that recognizecertain ions and allow for the nucleation and growth of the same.Non-limiting examples of templates include the polymers describedherein.

“Nucleation” refers to the process of forming a solid from solubilizedparticles, for example forming a nanowire in situ by converting asoluble precursor (e.g. metal and hydroxide ions) into nanocrystals inthe presence of a template.

“Nucleation site” refers to a site on a template, for example a polymer,where nucleation of ions may occur. Nucleation sites include, forexample, amino acids having carboxylic acid (—COOH), amino (—NH₃ ⁺ or—NH₂), hydroxyl (—OH), and/or thiol (—SH) functional groups.

“Anisotropic” means having an aspect ratio greater than one.

“Turnover number” is a measure of the number of reactant molecules acatalyst can convert to product molecules per unit time.

“Dopant” or “doping agent” is an impurity added to or incorporatedwithin a catalyst to optimize catalytic performance (e.g. increase ordecrease catalytic activity). As compared to the undoped catalyst, adoped catalyst may increase or decrease the selectivity, conversion,and/or yield of a reaction catalyzed by the catalyst.

“Atomic percent” (at % or at/at) or “atomic ratio” when used in thecontext of nanowire dopants refers to the ratio of the total number ofdopant atoms to the total number of metal atoms in the nanowire. Forexample, the atomic percent of dopant in a lithium doped Mg₆MnO₈nanowire is determined by calculating the total number of lithium atomsand dividing by the sum of the total number of magnesium and manganeseatoms and multiplying by 100 (i.e., atomic percent of dopant=[Liatoms/(Mg atoms+Mn atoms)]×100).

“Weight percent” (wt/wt)” when used in the context of nanowire dopantsrefers to the ratio of the total weight of dopant to the total combinedweight of thedopant and the nanowire. For example, the weight percent ofdopant in a lithium doped Mg₆MnO₈ nanowire is determined by calculatingthe total weight of lithium and dividing by the sum of the totalcombined weight of lithium and Mg₆MnO₈ and multiplying by 100 (i.e.,weight percent of dopant=[Li weight/(Li weight+Mg₆MnO₈ weight)]×100).

“Group 1” elements include lithium (Li), sodium (Na), potassium (K),rubidium (Rb), cesium (Cs), and francium (Fr).

“Group 2” elements include beryllium (Be), magnesium (Mg), calcium (Ca),strontium (Sr), barium (Ba), and radium (Ra).

“Group 3” elements include scandium (Sc) and yttrium (Y).

“Group 4” elements include titanium (Ti), zirconium (Zr), halfnium (Hf),and rutherfordium (Rf).

“Group 5” elements include vanadium (V), niobium (Nb), tantalum (Ta),and dubnium (Db).

“Group 6” elements include chromium (Cr), molybdenum (Mo), tungsten (W),and seaborgium (Sg).

“Group 7” elements include manganese (Mn), technetium (Tc), rhenium(Re), and bohrium (Bh).

“Group 8” elements include iron (Fe), ruthenium (Ru), osmium (Os), andhassium (Hs).

“Group 9” elements include cobalt (Co), rhodium (Rh), iridium (Ir), andmeitnerium (Mt).

“Group 10” elements include nickel (Ni), palladium (Pd), platinum (Pt)and darmistadium (Ds).

“Group 11” elements include copper (Cu), silver (Ag), gold (Au), androentgenium (Rg).

“Group 12” elements include zinc (Zn), cadmium (Cd), mercury (Hg), andcopernicium (Cn).

“Lanthanides” include lanthanum (La), cerium (Ce), praseodymium (Pr),neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu),gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium(Er), thulium (Tm), yitterbium (Yb), and lutetium (Lu).

“Actinides” include actinium (Ac), thorium (Th), protactinium (Pa),uranium (U), neptunium (Np), plutonium (Pu), americium (Am), curium(Cm), berklelium (Bk), californium (Cf), einsteinium (Es), fermium (Fm),mendelevium (Md), nobelium (No), and lawrencium (Lr).

“Metal element” or “metal” is any element, except hydrogen, selectedfrom Groups 1 through 12, lanthanides, actinides, aluminum (Al), gallium(Ga), indium (In), tin (Sn), thallium (Tl), lead (Pb), and bismuth (Bi).Metal elements include metal elements in their elemental form as well asmetal elements in an oxidized or reduced state, for example, when ametal element is combined with other elements in the form of compoundscomprising metal elements. For example, metal elements can be in theform of hydrates, salts, oxides, as well as various polymorphs thereof,and the like.

“Semi-metal element” refers to an element selected from boron (B),silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium(Te), and polonium (Po).

“Non-metal element” refers to an element selected from carbon (C),nitrogen (N), oxygen (O), fluorine (F), phosphorus (P), sulfur (S),chlorine (Cl), selenium (Se), bromine (Br), iodine (I), and astatine(At).

“C₂” refers to a hydrocarbon (i.e., compound consisting of carbon andhydrogen atoms) having only two carbon atoms, for example ethane andethylene. Similarily, “C3” refers to a hydrocarbon having only 3 carbonatoms, for example propane and propylene.

“Conversion” means the mole fraction (i.e., percent) of a reactantconverted to a product or products.

“Selectivity” refers to the percent of converted reactant that went to aspecified product, e.g., C2 selectivity is the % of converted methanethat formed ethane and ethylene, C3 selectivity is the % of convertedmethane that formed propane and propylene, CO selectivity is the % ofconverted methane that formed CO.

“Yield” is a measure of (e.g. percent) of product obtained relative tothe theoretical maximum product obtainable. Yield is calculated bydividing the amount of the obtained product in moles by the theoreticalyield in moles. Percent yield is calculated by multiplying this value by100. C2 yield is defined as the sum of the ethane and ethylene molarflow at the reactor outlet multiplied by two and divided by the inletmethane molar flow. C3 yield is defined as the sum of propane andpropylene molar flow at the reactor outlet multiplied by three anddivided by the inlet methane molar flow. C2+ yield is the sum of the C2yield and C3 yield. Yield is also calculable by multiplying the methaneconversion by the relevant selectivity, e.g. C2 yield is equal to themethane conversion times the C2 selectivity.

“Bulk catalyst” or “bulk material” means a catalyst prepared bytraditional techniques, for example by milling or grinding largecatalyst particles to obtain smaller/higher surface area catalystparticles. Bulk materials are prepared with minimal control over thesize and/or morphology of the material.

“Alkane” means a straight chain or branched, noncyclic or cyclic,saturated aliphatic hydrocarbon. Alkanes include linear, branched andcyclic structures. Representative straight chain alkanes includemethane, ethane, n-propane, n-butane, n-pentane, n-hexane, and the like;while branched alkanes include isopropane, sec-butane, isobutanel,tert-butane, isopentane, and the like. Representative cyclic alkanesinclude cyclopropane, cyclobutane, cyclopentane, cyclohexane, and thelike. “Alkene” means a straight chain or branched, noncyclic or cyclic,unsaturated aliphatic hydrocarbon having at least one carbon-carbondouble bond. Alkenes include linear, branched and cyclic structures.Representative straight chain and branched alkenes include ethylene,propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene,3-methyl-1-butene, 2-methyl-2-butene, 2,3-dimethyl-2-butene, and thelike. Cyclic alkenes include cyclohexene and cyclopentene and the like.

“Alkyne” means a straight chain or branched, noncyclic or cyclic,unsaturated aliphatic hydrocarbon having at least one carbon-carbontriple bond. Alkynes include linear, branched and cyclic structures.Representative straight chain and branched alkynes include acetylene,propyne, 1-butyne, 2-butyne, 1-pentyne, 2-pentyne, 3-methyl-1-butyne,and the like. Representative cyclic alkynes include cycloheptyne and thelike.

“Alkyl,” “alkenyl” and “alkynyl” refers to an alkane, alkene or alkyneradical, respectively.

“Aromatic” means a carbocyclic moiety having a cyclic system ofconjugated p orbitals forming a delocalized conjugated π system and anumber of π electrons equal to 4n+2 with n=0, 1, 2, 3, etc.Representative examples of aromatics include benzene and naphthalene andtoluene. “Aryl” refers to an aromatic radical. Exemplary aryl groupsinclude, but are not limited to, phenyl, napthyl and the like.

“Carbon-containing compounds” are compounds that comprise carbon.Non-limiting examples of carbon-containing compounds includehydrocarbons, CO and CO₂.

1. Structure/Physical Characteristics

As noted above, disclosed herein are nanowires useful as catalysts.Catalytic nanowires, and methods for preparing the same, are alsodescribed in PCT Pub. No. 2011/149996 and U.S. application Ser. No.______, filed on Nov. 29, 2012, and entitled “Nanowire Catalysts andMethods For Their Use and Preparation,” the full disclosures of whichare incorporated herein by reference in their entireties. FIG. 3 is aschematic representation of a representative nanowire 200. Typically,the nanowire is not uniform in its thickness or diameter. At any givenlocation along the nanowire backbone, a diameter (240 a, 240 b, 240 c,240 d) is the longest dimension of a cross section of the nanowire,i.e., is perpendicular to the axis of the nanowire backbone). FIG. 4 isa schematic representation of the nanowire 250, which shows non-uniformdiameters (280 a, 280 b, 280 c and 280 d).

As noted above, in some embodiments nanowires having a “bent” morphology(i.e. “bent nanowires”) are provided. A “bent’ morphology means that thebent nanowires comprise various twists, bends and/or kinks in theirgeneral morphology as illustrated generally in FIG. 3 and discussedabove. Bent nanowires have a ratio of effective length to actual lengthof less than one. Accordingly, in some embodiments the presentdisclosure provides nanowires having a ratio of effective length toactual length of less than one. In other embodiments, the nanowires havea ratio of effective length to actual length of between 0.99 and 0.01,between 0.9 and 0.1, between 0.8 and 0.2, between 0.7 and 0.3, orbetween 0.6 and 0.4. In other embodiments, the ratio of effective lengthto actual length is less than 0.99, less than 0.9, less than 0.8, lessthan 0.7, less than 0.6, less than 0.5, less than 0.4, less than 0.3,less than 0.2 or less than 0.1. In other embodiments, the ratio ofeffective length to actual length is less than 1.0 and more than 0.9,less than 1.0 and more than 0.8, less than 1.0 and more than 0.7, lessthan 1.0 and more than 0.6, less than 1.0 and more than 0.5, less than1.0 and more than 0.4, less than 1.0 and more than 0.3, less than 1.0and more than 0.2, or less than 1.0 and more than 0.1.

The ratio of effective length to actual length of a nanowire having abent morphology may vary depending on the angle of observation. Forexample, one-skilled in the art will recognize that the same nanowire,when observed from different perspectives, can have a differenteffective length as determined by TEM. In addition, not all nanowireshaving a bent morphology will have the same ratio of effective length toactual length. Accordingly, in a population (i.e. plurality) ofnanowires having a bent morphology, a range of ratios of effectivelength to actual length is expected. Although the ratio of effectivelength to actual length may vary from nanowire to nanowire, nanowireshaving a bent morphology will always have a ratio of effective length toactual length of less than one from any angle of observation.

In various embodiments, a substantially straight nanowire is provided. Asubstantially straight nanowire has a ratio of effective length toactual length equal to one. Accordingly, in some embodiments, thenanowires of the present disclosure have a ratio of effective length toactual length equal to one.

The actual lengths of the nanowires disclosed herein may vary. Forexample in some embodiments, the nanowires have an actual length ofbetween 100 nm and 100 μm. In other embodiments, the nanowires have anactual length of between 100 nm and 10 μm. In other embodiments, thenanowires have an actual length of between 200 nm and 10 μm. In otherembodiments, the nanowires have an actual length of between 500 nm and 5μm. In other embodiments, the actual length is greater than 5 μm. Inother embodiments, the nanowires have an actual length of between 800 nmand 1000 nm. In other further embodiments, the nanowires have an actuallength of 900 nm. As noted below, the actual length of the nanowires maybe determined by TEM, for example, in bright field mode at 5 keV.

The diameter of the nanowires may be different at different points alongthe nanowire backbone. However, the nanowires comprise a mode diameter(i.e. the most frequently occurring diameter). As used herein, thediameter of a nanowire refers to the mode diameter. In some embodiments,the nanowires have a diameter of between 1 nm and 10 μm, between 1 nmand 1 μm, between 1 nm and 500 nm, between 1 nm and 100 nm, between 7 nmand 100 nm, between 7 nm and 50 nm, between 7 nm and 25 nm, or between 7nm and 15 nm. On other embodiments, the diameter is greater than 500 nm.As noted below, the diameter of the nanowires may be determined by TEM,for example, in bright field mode at 5 keV.

Various embodiments of the present disclosure provide nanowires havingdifferent aspect ratios. In some embodiments, the nanowires have anaspect ratio of greater than 10:1. In other embodiments, the nanowireshave an aspect ratio greater than 20:1. In other embodiments, thenanowires have an aspect ratio greater than 50:1. In other embodiments,the nanowires have an aspect ratio greater than 100:1.

In some embodiments, the nanowires comprise a solid core while in otherembodiments, the nanowires comprise a hollow core.

The morphology of a nanowire (including length, diameter, and otherparameters) can be determined by transmission electron microscopy (TEM).Transmission electron microscopy (TEM) is a technique whereby a beam ofelectrons is transmitted through an ultra thin specimen, interactingwith the specimen as it passes through. An image is formed from theinteraction of the electrons transmitted through the specimen. The imageis magnified and focused onto an imaging device, such as a fluorescentscreen, on a layer of photographic film or detected by a sensor such asa CCD camera. TEM techniques are well known to those of skill in theart.

A TEM image of nanowires may be taken, for example, in bright field modeat 5 keV.

The nanowires of the present disclosure can be further characterized bypowder x-ray diffraction (XRD). XRD is a technique capable of revealinginformation about the crystallographic structure, chemical composition,and physical properties of materials, including nanowires. XRD is basedon observing the diffracted intensity of an X-ray beam hitting a sampleas a function of incident and diffraction angle, polarization, andwavelength or energy.

Crystal structure, composition, and phase, including the crystal domainsize of the nanowires, can be determined by XRD. In some embodiments,the nanowires comprise a single crystal domain (i.e. singlecrystalline). In other embodiments, the nanowires comprise multiplecrystal domains (i.e. polycrystalline). In some other embodiments, theaverage crystal domain of the nanowires is less than 100 nm, less than50 nm, less than 30 nm, less than 20 nm, less than 10 nm, less than 5nm, or less than 2 nm.

Typically, a catalytic material described herein comprises a pluralityof nanowires. In certain embodiments, the plurality of nanowires form amesh of randomly distributed and, to various degrees, interconnectednanowires. FIG. 5 is a schematic representation of a nanowire mesh 300.

The total surface area per gram of a nanowire or plurality of nanowiresmay have an effect on the catalytic performance. Pore size distributionmay affect the nanowires catalytic performance as well. Surface area andpore size distribution of the nanowires or plurality of nanowires can bedetermined by BET (Brunauer, Emmett, Teller) measurements. BETtechniques utilize nitrogen adsorption at various temperatures andpartial pressures to determine the surface area and pore sizes ofcatalysts. BET techniques for determining surface area and pore sizedistribution are well known in the art.

In some embodiments the nanowires have a surface area of between 0.0001and 3000 m²/g, between 0.0001 and 2000 m²/g, between 0.0001 and 1000m²/g, between 0.0001 and 500 m²/g, between 0.0001 and 100 m²/g, between0.0001 and 50 m²/g, between 0.0001 and 20 m²/g, between 0.0001 and 10m²/g or between 0.0001 and 5 m²/g.

In some embodiments the nanowires have a surface area of between 0.001and 3000 m²/g, between 0.001 and 2000 m²/g, between 0.001 and 1000 m²/g,between 0.001 and 500 m²/g, between 0.001 and 100 m²/g, between 0.001and 50 m²/g, between 0.001 and 20 m²/g, between 0.001 and 10 m²/g orbetween 0.001 and 5 m²/g.

In some other embodiments the nanowires have a surface area of between2000 and 3000 m²/g, between 1000 and 2000 m²/g, between 500 and 1000m²/g, between 100 and 500 m²/g, between 10 and 100 m²/g, between 5 and50 m²/g, between 2 and 20 m²/g or between 0.0001 and 10 m²/g.

In other embodiments, the nanowires have a surface area of greater than2000 m²/g, greater than 1000 m²/g, greater than 500 m²/g, greater than100 m²/g, greater than 50 m²/g, greater than 20 m²/g, greater than 10m²/g, greater than 5 m²/g, greater than 1 m²/g, greater than 0.0001m²/g.

2. Chemical Composition

As noted above, disclosed herein are nanowires useful as catalysts. Thecatalytic nanowires may have any number of compositions andmorphologies. In some embodiments, the nanowires are inorganic. In otherembodiments, the nanowires are polycrystalline. In some otherembodiments, the nanowires are inorganic and polycrystalline. In yetother embodiments, the nanowires are single-crystalline, or in otherembodiments the nanowires are inorganic and single-crystalline. In stillother embodiments of any of the foregoing, the nanowires may have aratio of effective length to actual length of less than one and anaspect ratio of greater than ten as measured by TEM in bright field modeat 5 keV. In still other embodiments of any of the forgoing, thenanowires may comprise one or more elements from any of Groups 1 through7, lanthanides, actinides or combinations thereof.

In some embodiments, the nanowires comprise one or more metal elementsfrom any of Groups 1-7, lanthanides, actinides or combinations thereof,for example, the nanowires may be mono-metallic, bi-metallic,tri-metallic, etc (i.e. contain one, two, three, etc. metal elements).In some embodiments, the metal elements are present in the nanowires inelemental form while in other embodiments the metal elements are presentin the nanowires in oxidized form. In other embodiments the metalelements are present in the nanowires in the form of a compoundcomprising a metal element. The metal element or compound comprising themetal element may be in the form of oxides, hydroxides, oxyhydroxides,salts, hydrated oxides, carbonates, oxy-carbonates, sulfates,phosphates, acetates, oxalates and the like. The metal element orcompound comprising the metal element may also be in the form of any ofa number of different polymorphs or crystal structures.

In certain examples, metal oxides may be hygroscopic and may changeforms once exposed to air, may absorb carbon dioxide, may be subjectedto incomplete calcination or any combination thereof. Accordingly,although the nanowires are often referred to as metal oxides, in certainembodiments the nanowires also comprise hydrated oxides, oxyhydroxides,hydroxides, oxycarbonates (or oxide carbonates), carbonates orcombinations thereof.

In other embodiments, the nanowires comprise one or more metal elementsfrom Group 1. In other embodiments, the nanowires comprise one or moremetal elements from Group 2. In other embodiments, the nanowirescomprise one or more metal elements from Group 3. In other embodiments,the nanowires comprise one or more metal elements from Group 4. In otherembodiments, the nanowires comprise one or more metal elements fromGroup 5. In other embodiments, the nanowires comprise one or more metalelements from Group 6. In other embodiments, the nanowires comprise oneor more metal elements from Group 7. In other embodiments, the nanowirescomprise one or more metal elements from the lanthanides. In otherembodiments, the nanowires comprise one or more metal elements from theactinides.

In one embodiment, the nanowires comprise one or more metal elementsfrom any of Groups 1-7, lanthanides, actinides or combinations thereofin the form of an oxide. In another embodiment, the nanowires compriseone or more metal elements from Group 1 in the form of an oxide. Inanother embodiment, the nanowires comprise one or more metal elementsfrom Group 2 in the form of an oxide. In another embodiment, thenanowires comprise one or more metal elements from Group 3 in the formof an oxide. In another embodiment, the nanowires comprise one or moremetal elements from Group 4 in the form of an oxide. In anotherembodiment, the nanowires comprise one or more metal elements from Group5 in the form of an oxide. In another embodiment, the nanowires compriseone or more metal elements from Group 6 in the form of an oxide. Inanother embodiment, the nanowires comprise one or more metal elementsfrom Group 7 in the form of an oxide. In another embodiment, thenanowires comprise one or more metal elements from the lanthanides inthe form of an oxide. In another embodiment, the nanowires comprise oneor more metal elements from the actinides in the form of an oxide.

In other embodiments, the nanowires comprise oxides, hydroxides,sulfates, carbonates, oxide carbonates, acetates, oxalates, phosphates(including hydrogenphosphates and dihydrogenphosphates), oxyhalides,hydroxihalides, oxyhydroxides, oxysulfates or combinations thereof ofone or more metal elements from any of Groups 1-7, lanthanides,actinides or combinations thereof. In some other embodiments, thenanowires comprise oxides, hydroxides, sulfates, carbonates, oxidecarbonates, oxalates or combinations thereof of one or more metalelements from any of Groups 1-7, lanthanides, actinides or combinationsthereof. In other embodiments, the nanowires comprise oxides, and inother embodiments, the nanowires comprise hydroxides. In otherembodiments, the nanowires comprise carbonates, and in otherembodiments, the nanowires comprise oxy-carbonates. In otherembodiments, the nanowires comprise Li₂CO₃, LiOH, Li₂O, Li₂C₂O₄, Li₂SO₄,Na₂CO₃, NaOH, Na₂O, Na₂C₂O₄, Na₂SO₄, K₂CO₃, KOH, K₂O, K₂C₂O₄, K₂SO₄,Cs₂CO₃, CsOH, Cs₂O, CsC₂O₄, CsSO₄, Be(OH)₂, BeCO₃, BeO, BeC₂O₄. BeSO₄,Mg(OH)₂, MgCO₃, MgO, MgC₂O₄. MgSO₄, Ca(OH)₂, CaO, CaCO₃, CaC₂O₄, CaSO₄,Y₂O₃, Y₃(CO₃)₂, Y(OH)₃, Y₂(C₂O4)₃, Y₂(SO4)₃, Zr(OH)₄, ZrO(OH)₂, ZrO2,Zr(C₂O₄)₂, Zr(SO₄)₂, Ti(OH)₄, TiO(OH)₂, TiO2, Ti(C₂O₄)₂, Ti(SO₄)₂, BaO,Ba(OH)₂, BaCO₃, BaC₂O₄, BaSO₄, La(OH)₃, La₂O₃, La₂(C₂O₄)₃, La₂(SO₄)₃,La₂(CO₃)₃, Ce(OH)₄, CeO₂, Ce₂O₃, Ce(C₂O₄)₂, Ce(SO₄)₂, Ce(CO₃)₂, ThO₂,Th(OH)₄, Th(C₂O₄)₂, Th(SO₄)₂, Th(CO₃)₂, Sr(OH)₂, SrCO₃, SrO, SrC₂O₄,SrSO₄, Sm₂O₃, Sm(OH)₃, Sm₂(CO₃)₃, Sm₂(C₂O₃)₃, Sm₂(SO₄)₃, LiCa₂Bi₃O₄Cl₆,NaMnO₄, Na₂WO₄, NaMn/WO₄, CoWO₄, CuWO₄, K/SrCoO₃, K/Na/SrCoO₃,Na/SrCoO₃, Li/SrCoO₃, SrCoO₃, Mg₆MnO₈, LiMn₂O₄, Li/Mg₆MnO₈,Na₁₀Mn/W₅O₁₇, Mg₃Mn₃B₂O₁₀, Mg₃(BO₃)₂, molybdenum oxides, molybdenumhydroxides, molybdenum oxalates, molybdenum sulfates, Mn₂O₃, Mn₃O₄,manganese oxides, manganese hydroxides, manganese oxalates, manganesesulfates, manganese tungstates, manganese carbonates, vanadium oxides,vanadium hydroxides, vanadium oxalates, vanadium sulfates, tungstenoxides, tungsten hydroxides, tungsten oxalates, tungsten sulfates,neodymium oxides, neodymium hydroxides, neodymium carbonates, neodymiumoxalates, neodymium sulfates, europium oxides, europium hydroxides,europium carbonates, europium oxalates, europium sulfates, praseodymiumoxides, praseodymium hydroxides, praseodymium carbonates, praseodymiumoxalates, praseodymium sulfates, rhenium oxides, rhenium hydroxides,rhenium oxalates, rhenium sulfates, chromium oxides, chromiumhydroxides, chromium oxalates, chromium sulfates, potassium molybdenumoxides/silicon oxide or combinations thereof.

In other embodiments, the nanowires comprise Li₂O, Na₂O, K₂O, Cs₂O, BeOMgO, CaO, ZrO(OH)₂, ZrO2, TiO₂, TiO(OH)₂, BaO, Y₂O₃, La₂O₃, CeO₂, Ce₂O₃,ThO₂, SrO, Sm₂O₃, Nd₂O₃, Eu₂O₃, Pr₂O₃, LiCa₂Bi₃O₄Cl₆, NaMnO₄, Na₂WO₄,Na/Mn/WO₄, Na/MnWO₄, Mn/WO4, K/SrCoO₃, K/Na/SrCoO₃, K/SrCoO₃, Na/SrCoO₃,Li/SrCoO₃, SrCoO₃, Mg₆MnO₈, Na/B/Mg₆MnO₈, Li/B/Mg₆MnO₈, Zr₂Mo₂O₈,molybdenum oxides, Mn₂O₃, Mn₃O₄, manganese oxides, vanadium oxides,tungsten oxides, neodymium oxides, rhenium oxides, chromium oxides, orcombinations thereof.

In still other aspects, the nanowires comprise lanthanide containingperovskites. A perovskite is any material with the same type of crystalstructure as calcium titanium oxide (CaTiO₃). Examples of perovskiteswithin the context of the present disclosure include, but are notlimited to, LaCoO₃ and La/SrCoO₃.

In other embodiments, the nanowires comprise TiO₂, Sm₂O₃, V₂O₅, MoO₃,BeO, MnO₂, MgO, La₂O₃, Nd₂O₃, Eu₂O₃, ZrO₂, SrO, Na₂WO₄, Mn/WO₄, BaO,Mn₂O₃, Mn₃O₄, Mg₆MnO₈, Na/B/Mg₆MnO₈, Li/B/Mg₆MnO₈, NaMnO₄, CaO orcombinations thereof. In further embodiments, the nanowires compriseMgO, La₂O₃, Nd₂O₃, Na₂WO₄, Mn/WO₄, Mn₂O₃, Mn₃O₄, Mg₆MnO₈, Na/B/Mg₆MnO₈,Li/B/Mg₆MnO₈ or combinations thereof.

In some embodiments, the nanowires comprises Mg, Ca, Sr, Ba, Y, La, W,Mn, Mo, Nd, Sm, Eu, Pr, Zr or combinations thereof, and in otherembodiments the nanowire comprises MgO, CaO, SrO, BaO, Y₂O₃, La₂O₃,Na₂WO₄, Mn₂O₃, Mn₃O₄, Nd₂O₃, Sm₂O₃, Eu₂O₃, Pr₂O₃, Mg₆MnO₈, NaMnO₄,Na/Mn/W/O, Na/MnWO₄, MnWO₄ or combinations thereof.

In more specific embodiments, the nanowires comprise MgO. In otherspecific embodiments, the nanowires comprise CaO. In other embodiments,the nanowires comprise SrO. In other specific embodiments, the nanowirescomprise La₂O₃. In other specific embodiments, the nanowires compriseNa₂WO₄ and may optionally further comprise Mn/WO₄. In other specificembodiments, the nanowires comprise Mn₂O₃. In other specificembodiments, the nanowires comprise Mn₃O₄. In other specificembodiments, the nanowires comprise Mg₆MnO₈. In other specificembodiments, the nanowires comprise NaMnO₄. In other specificembodiments, the nanowires comprise Nd₂O₃. In other specificembodiments, the nanowires comprise Eu₂O₃. In other specificembodiments, the nanowires comprise Pr₂O₃. In some other embodiments,the nanowires comprise Sm₂O₃.

In certain embodiments, the nanowires comprise an oxide of a group 2element. For example, in some embodiments, the nanowires comprise anoxide of magnesium. In other embodiments, the nanowires comprise anoxide of calcium. In other embodiments, the nanowires comprise an oxideof strontium. In other embodiments, the nanowires comprise an oxide ofbarium.

In certain other embodiments, the nanowires comprise an oxide of a group3 element. For example, in some embodiments, the nanowires comprise anoxide of yttrium. In other embodiments, the nanowires comprise an oxideof scandium.

In yet other certain embodiments, the nanowires comprise an oxide of anearly lanthanide element. For example, in some embodiments, thenanowires comprise an oxide of lanthanum. In other embodiments, thenanowires comprise an oxide of cerium. In other embodiments, thenanowires comprise an oxide of praseodymium. In other embodiments, thenanowires comprise an oxide of neodymium. In other embodiments, thenanowires comprise an oxide of promethium. In other embodiments, thenanowires comprise an oxide of samarium. In other embodiments, thenanowires comprise an oxide of europium. In other embodiments, thenanowires comprise an oxide of gadolinium.

In certain other embodiments, the nanowires comprise a lanthanide in theform of an oxy-carbonate. For example, the nanowires may compriseLn₂O₂(CO₃), where Ln represents a lanthanide. Examples in this regardinclude: La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Luoxy-carbonates. In other embodiments, the nanowires comprise anoxy-carbonate of one or more elements from any of Groups 1 through 7,lanthanides, actinides or combinations thereof. Accordingly in oneembodiment the nanowires comprise Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr,Ba, Ra, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc or Reoxy-carbonate. In other embodiments, the nanowires comprise Ac, Th, U orPa oxide carbonate. An oxy-carbonate may be represented by the followingformula: M_(x)O_(y)(CO₃)_(z), wherein M is a metal element from any ofGroups 1 through 7, lanthanides or actinides and x, y and z areintergers such that the overall charge of the metal oxy-carbonate isneutral.

In certain other embodiments, the nanowires comprise a carbonate of agroup 2 element. For example, the nanowires may comprise MgCO₃, CaCO₃,SrCO₃, BaCO₃ or combination thereof. In other embodiments, the nanowirescomprise a carbonate of one or more elements from any of the Group 1through 7, lanthanides and actinides or combination thereof. Accordinglyin one embodiment the nanowires comprise a Li, Na, K, Rb, Cs, Fr, Be,Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re,La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ac, Th, Paor U carbonate.

In other embodiments, the nanowires comprise TiO₂, Sm₂O₃, V₂O₅, MoO₃,BeO, MnO₂, MgO, La₂O₃, ZrO₂, SrO, Na₂WO₄, BaCO₃, Mn₂O₃, Mn₃O₄, Mg₆MnO₈,Na/B/Mg₆MnO₈, Li/B/Mg₆MnO₈, Zr₂Mo₂O₈, NaMnO₄, CaO or combinationsthereof and further comprise one or more dopants comprised of metalelements, semi-metal elements, non-metal elements or combinationsthereof. In some further embodiments, the nanowires comprise MgO, La₂O₃,Na₂WO₄, Mn₂O₃, Mn₃O₄, Mg₆MnO₈, Zr₂Mo₂O₈, NaMnO₄ or combinations thereof,and the nanowires further comprise Li, Sr, Zr, Ba, Mn or Mn/WO₄. In someembodiments, the nanowires or a catalytic material comprising aplurality of the nanowires comprise a combination of one or more ofmetal elements from any of Groups 1-7, lanthanides or actinides and oneor more of metal elements, semi-metal elements or non-metal elements.For example in one embodiment, the nanowires comprise the combinationsof Li/Mg/O, Ba/Mg/O, Zr/La/O, Ba/La/O, Sr/La/O, Zr/V/P/O, Mo/V/Sb/O,V₂O₅/Al₂O₃, Mo/V/O, V/Ce/O, V/Ti/P/O, V₂O₅/TiO₂, V/P/O/TiO₂,V/P/O/Al₂O₃, V/Mg/O, V₂O₅/ZrO₂, Mo/V/Te/O, V/Mo/O/Al₂O₃, Ni/V/Sb/O,Co/V/Sb/O, Sn/V/Sb/O, Bi/V/Sb/O, Mo/V/Te/Nb/O, Mo/V/Nb/O, V₂O₅/MgO/SiO₂,V/Co, MoO₃/Al₂O₃, Ni/Nb/O, NiO/Al₂O₃, Ga/Cr/Zr/P/O, MoO₃/Cl/SiO₂/TiO₂,Co/Cr/Sn/W/O, Cr/Mo/O, MoO₃/Cl/SiO₂/TiO₂, Co/Ca, NiO/MgO, MoO₃/Al₂O₃,Nb/P/Mo/O, Mo/V/Te/Sb//Nb/O, La/Na/Al/O, Ni/Ta/Nb/O, Mo/Mn/V/W/O,Li/Dy/Mg/O, Sr/La/Nd/O, Co/Cr/Sn/W/O, MoO₃/SiO₂/TiO₂, Sm/Na/P/O,Sm/Sr/O, Sr/La/Nd/O, Co/P/O/TiO₂, La/Sr/Fe/Cl/O, La/Sr/Cu/Cl/O,Y/Ba/Cu/O, Na/Ca/O, V₂O₅/ZrO₂, V/Mg/O, Mn/V/Cr/W/O/Al₂O₃, V₂O₅/K/SiO₂,V₂O₅/Ca/TiO₂, V₂O₅/K/TiO₂, V/Mg/Al/O, V/Zr/O, V/Nb/O, V₂O₅/Ga₂O₃,V/Mg/Al/O, V/Nb/O, V/Sb/O, V/Mn/O, V/Nb/O/Sb₂O₄, V/Sb/O/TiO₂, V₂O₅/Ca,V₂O₅/K/Al₂O₃, V₂O₅/TiO₂, V₂O₅/MgO/TiO₂, V₂O₅/ZrO₂, V/Al/F/O,V/Nb/O/TiO₂, Ni/V/O, V₂O₅/SmVO₄, V/W/O, V₂O₅/Zn/Al₂O₃, V₂O₅/CeO₂,V/Sm/O, V₂O₅/TiO₂/SiO₂, Mo/Li/O/Al₂O₃, Mg/Dy/Li/Cl/O, Mg/Dy/Li/Cl/O,Ce/Ni/O, Ni/Mo/O/V, Ni/Mo/O/V/N, Ni/Mo/O Sb/O/N, MoO₃/Cl/SiO₂/TiO₂,Co/Mo/O, Ni/Ti/O, Ni/Zr/O, Cr/O, MoO₃/Al₂O₃, Mn/P/O, MoO₃/K/ZrO₂,Na/W/O, Mn/Na/W/O, Mn/Na//W/O/SiO₂, Na/W/O/SiO₂, Mn/Mo/O, Nb₂O₅/TiO₂,Co/W/O, Ni/Mo/O, Ga/Mo/O, Mg/Mo/V/O, Cr₂O₃/Al₂O₃, Cr/Mo/Cs/O/Al₂O₃,Co/Sr/O/Ca, Ag/Mo/P/O, MoO₃/SmVO₄, Mo/Mg/Al/O, MoO₃/K/SiO₂/TiO₂,Cr/Mo/O/Al₂O₃, MoO₃/Al₂O₃, Ni/Co/Mo/O, Y/Zr/O, Y/Hf, Zr/Mo/Mn/O,Mg/Mn/O, Li/Mn/O, Mg/Mn/B/O, Mg/B/O, Na/B/Mg/Mn/O, Li/B/Mg/Mn/O,Mn/Na/P/O, Na/Mn/Mg/O, Zr/Mo/O, Mn/W/O or Mg/Mn/O.

In a specific embodiment, the nanowires comprise the combinations ofLi/Mg/O, Ba/Mg/O, Zr/La/O, Ba/La/O, Sr/La/O, Sr/Nd/O, La/O, Nd/O, Eu/O,Mg/La/O, Mg/Nd/O, Na/La/O, Na/Nd/O, Sm/O, Mn/Na/W/O, Mg/Mn/O,Na/B/Mg/Mn/O, Li/B/Mg/Mn/O, Zr/Mo/O or Na/Mn/Mg/O. For example, in someembodiments the nanowires comprise the combinations of Li/MgO, Ba/MgO,Sr/La₂O₃, Ba/La₂O₃, Mn/Na₂WO₄, Mn/Na₂WO₄/SiO₂, Mn₂O₃/Na₂WO₄,Mn₃O₄/Na₂WO₄, Li/B/Mg₆MnO₈, Na/B/Mg₆MnO₈ or NaMnO₄/MgO. In certainembodiments, the nanowire comprises Li/MgO, Ba/MgO, Sr/La₂O₃,Mg/Na/La₂O₃, Sr/Nd₂O₃, or Mn/Na₂WO₄.

In some other specific embodiments, the nanowires comprise thecombination of Li/MgO. In other specific embodiments, the nanowirescomprise the combination of Ba/MgO. In other specific embodiments, thenanowires comprise the combination of Sr/La₂O₃. In other specificembodiments, the nanowires comprise the combination of Ba/La₂O₃. Inother specific embodiments, the nanowires comprise the combination ofMn/Na₂WO₄. In other specific embodiments, the nanowires comprise thecombination of Mn/Na₂WO₄/SiO₂. In other specific embodiments, thenanowires comprise the combination of Mn₂O₃/Na₂WO₄. In other specificembodiments, the nanowires comprise the combination of Mn₃O₄/Na₂WO₄. Inother specific embodiments, the nanowires comprise the combination ofMn/WO₄/Na₂WO₄. In other specific embodiments, the nanowires comprise thecombination of Li/B/Mg₆MnO₈. In other specific embodiments, thenanowires comprise the combination of Na/B/Mg₆MnO₈. In other specificembodiments, the nanowires comprise the combination of NaMnO₄/MgO.

Polyoxyometalates (POM) are a class of metal oxides that range instructure from the molecular to the micrometer scale. The uniquephysical and chemical properties of POM clusters, and the ability totune these properties by synthetic means have attracted significantinterest from the scientific community to create “designer” materials.For example, heteropolyanions such as the well-known Keggin [XM₁₂O₄₀]⁻and Wells-Dawson [X₂M1₈O₆₂]⁻ anions (where M=W or Mo; and X=atetrahedral template such as but not limited to Si, Ge, P) andisopolyanions with metal oxide frameworks with general formulas[MO_(x)]_(n) where M=Mo, W, V, and Nb and x=4-7 are ideal candidates forOCM/ODH catalysts. Accordingly, in one embodiment the nanowires comprise[XM₁₂O₄₀]⁻ or [X₂M1₈O₆₂]⁻ anions (where M=W or Mo; and X=a tetrahedraltemplate such as but not limited to Si, Ge, P) and isopolyanions withmetal oxide frameworks with general formulas [MO_(x)]_(n) where M=Mo, W,V, and Nb and x=4-7. In some embodiments, X is P or Si.

These POM clusters have “lacunary” sites that can accommodate divalentand trivalent first row transition metals, the metal oxide clustersacting as ligands. These lacunary sites are essentially “doping” sites,allowing the dopant to be dispersed at the molecular level instead of inthe bulk which can create pockets of unevenly dispersed doped material.Because the POM clusters can be manipulated by standard synthetictechniques, POMs are highly modular and a wide library of materials canbe prepared with different compositions, cluster size, and dopantoxidation state. These parameters can be tuned to yield desired OCM/ODHcatalytic properties. Accordingly, one embodiment of the presentdisclosure is a nanowire comprising one or more POM clusters. Suchnanowires find utility as catalysts, for example, in the OCM and ODHreactions.

Silica doped sodium manganese tungstate (NaMn/WO₄/SiO₂) is a promisingOCM catalyst. The NaMn/WO₄/SiO₂ system is attractive due to its high C2selectivity and yield. Unfortunately, good catalytic activity is onlyachievable at temperatures greater than 800° C. and although the exactactive portion of the catalyst is still subject to debate, it is thoughtthat sodium plays an important role in the catalytic cycle. In addition,the NaMn/WO₄/SiO₂ catalyst surface area is relatively low <2 m²/g.Manganese tungstate (Mn/WO₄) nanorods (i.e., straight nanowires) can beused to model a NaMn/WO₄/SiO₂ based nanowire OCM catalyst. The Mn/WO₄nanorods are prepared hydro-thermally and the size can be tuned based onreaction conditions with dimensions of 25-75 nm in diameter to 200-800nm in length. The as-prepared nano-rods have higher surface areas thanthe NaMn/WO₄/SiO₂ catalyst systems. In addition, the amount of sodium,or other elements, can be precisely doped into the Mn/WO₄ nanorodmaterial to target optimal catalytic activity. Nanorod tungstate basedmaterials can be expanded to, but not limited to, CoWO₄ or CuWO₄materials, which may serve as base materials for OCM/ODH catalysis. Inaddition to straight nanowires, the above discussion applies to thedisclosed nanowires having a bent morphology as well. The nanowires ofthe disclosure may be analyzed by inductively coupled plasma massspectrometry (ICP-MS) to determine the element content of the nanowires.ICP-MS is a type of mass spectrometry that is highly sensitive andcapable of the determination of a range of metals and several non-metalsat concentrations below one part in 10¹². ICP is based on couplingtogether an inductively coupled plasma as a method of producing ions(ionization) with a mass spectrometer as a method of separating anddetecting the ions. ICP-MS methods are well known in the art.

In some embodiments, the nanowire comprises a combination of two or moremetal compounds, for example metal oxides. For example, in someembodiments, the nanowire comprises Mn₂O₃/Na₂WO₄,Mn₃O₄/Na₂WO₄MnWO₄/Na₂WO₄/Mn₂O₃, MnWO₄/Na₂WO₄/Mn₃O₄ or NaMnO₄/MgO.

Certain rare earth compositions have been found to be useful catalysts,for example as catalysts in the OCM reaction. Thus, in one embodiment,the nanowire catalysts comprise lanthanide oxides such as La₂O₃, Nd₂O₃,Yb₂O₃, Eu₂O₃ or Sm₂O₃. In other embodiments, the nanowires comprisemixed oxides of lanthanide metals. Such mixed oxides are represented byLn1_(4-x)Ln2_(x)O₆, wherein Ln1 and Ln2 are each independently alanthanide element and x is a number ranging from greater than 0 to lessthan 4. In other more specific embodiments, the lanthanide mixed oxidescomprise La_(4-x)Ln1_(x)O₆, wherein Ln1 is a lanthanide element and x isa number ranging from greater than 0 to less than 4. For example, insome embodiments the lanthanide mixed oxides are mixed oxides oflanthanum and neodymium and the nanowires comprise La_(4-x)Nd_(x)O₆,wherein x is a number ranging from greater than 0 to less than 4 havealso been found to be useful in the OCM reaction. For example La₃NdO₆,LaNd₃O₆, La_(1.5)Nd_(2.5)O₆, La_(2.5)Nd_(1.5)O₆, La_(3.2)Nd_(0.8)O₆,La_(3.5)Nd_(0.5)O₆, La_(3.8)Nd_(0.2)O₆, or combinations thereof havebeen found to be useful OCM catalyst compositions.

Any of the foregoing nanowire catalysts may have any morphology (e.g.,bent, straight, etc.) and may be prepared via any method describedherein or known in the art. For example, these nanowires may be preparedfrom any of the polymer templates described herein or known in the art.Also as discussed below, certain dopant combinations with the abovelanthanide nanowires have been found to be useful for enhancing thecatalytic activity of the nanowires.

In other embodiments the nanowires are in a core/shell arrangement (seebelow) and the nanowires comprise Eu on a MgO core; La on a MgO core; Ndon a MgO core; Sm on a MgO core; Y—Ce on a Na doped MgO core Na or Nadoped Ce—Y on a MgO core.

In an aspect of the invention, nanowires, and materials comprising thesame, having the empirical formula M4_(w)M5_(x)M6_(y)O, are provided,wherein each M4 is independently one or more elements selected fromGroups 1 through 4, each M5 is independently one or more elementsselected from Group 7 and M6 is independently one or more elementsselected from Groups 5 through 8 and Groups 14 through 15 and w, x, yand z are integers such that the overall charge is balanced.

In some embodiments, M4 comprises one or more elements selected fromGroup 1, such as sodium (Na), while M6 includes one or more elementsselected from Group 6, such as tungsten (W) and M5 is Mn. In anotherembodiment, M4 is Na, M5 is Mn, M6 is W, the ratio of w:x is 10:1, andthe ratio of w:y is 2:1. In such a case, the overall empirical formulaof the nanowire is Na₁₀MnW₅O_(z). When Na is in the +1 oxidation state,W is in the +6 oxidation state, and Mn is in the +4 oxidation state, zmust equal 17 so as to fill the valence requirements of Na, W and Mn. Asa result, the overall empirical formula of the nanowire in thisembodiment is Na₁₀MnW₅O₁₇.

In other embodiments, the ratios of w:x can be 1:1, or 5:1, or 15:1, or25:1, or 50:1. In yet other embodiments, for any given ratio of w:x, theratios of w:y can be 1:5, or 1:2, or 1:2, or 5:1. In still otherembodiments, any nanowire of the empirical formulaM4_(w)M5_(x)M6_(y)O_(z), including the nanowire of the empirical formulaM4₁₀MnM6₅O₁₇ described above, can be supported on an oxide substrate.Oxide substrates can include silica, alumina, and titania. The reactionthat anchors nanowire materials onto oxide substrates is analogous tothe reaction that anchors bulk materials onto oxide substrates, such asthat described in U.S. Pat. No. 4,808,563, which is entirelyincorporated herein by reference. Alternatively, non-oxide support, forexample silicon carbide can be used to support nanowires of the presentinvention, for example Na₁₀MnW₅O₁₇ nanowires and others. Silicon carbidehas very good high temperature stability and chemical inertness towardOCM reaction intermediates and thus is particularly effective as asupport in this reaction.

3. Catalytic Materials

As noted above, the present disclosure provides a catalytic materialcomprising a plurality of nanowires. In certain embodiments, thecatalytic material comprises a support or carrier. The support ispreferably porous and has a high surface area. In some embodiments thesupport is active (i.e. has catalytic activity). In other embodiments,the support is inactive (i.e. non-catalytic). In some embodiments, thesupport comprises an inorganic oxide, Al₂O₃, SiO₂, TiO₂, MgO, CaO, SrO,ZrO₂, ZnO, LiAlO₂, MgAl₂O₄, MnO, MnO₂, Mn₃O₄, La₂O₃, AlPO4, SiO₂/Al₂O₃,activated carbon, silica gel, zeolites, activated clays, activatedAl₂O₃, SiC, diatomaceous earth, magnesia, aluminosilicates, calciumaluminate, support nanowires or combinations thereof. In someembodiments the support comprises silicon, for example SiO₂. In otherembodiments the support comprises magnesium, for example MgO. In otherembodiments the support comprises zirconium, for example ZrO₂. In yetother embodiments, the support comprises lanthanum, for example La₂O₃.In yet other embodiments, the support comprises lanthanum, for exampleY₂O₃. In yet other embodiments, the support comprises hafnium, forexample HfO₂. In yet other embodiments, the support comprises aluminum,for example Al₂O₃. In yet other embodiments, the support comprisesgallium, for example Ga₂O₃.

In still other embodiments, the support material comprises an inorganicoxide, Al₂O₃, SiO₂, TiO₂, MgO, ZrO₂, HfO2, CaO, SrO, ZnO, LiAlO₂,MgAl₂O₄, MnO, MnO₂, Mn₂O₄, Mn₃O₄, La₂O₃, activated carbon, silica gel,zeolites, activated clays, activated Al₂O₃, diatomaceous earth,magnesia, aluminosilicates, calcium aluminate, support nanowires orcombinations thereof. For example, the support material may compriseSiO₂, ZrO₂, CaO, La₂O₃ or MgO.

In still other embodiments, the support material comprises a carbonate.For example, in some embodiments the support material comprises MgCO₃,CaCO₃, SrCO₃, BaCO₃, Y₂(CO₃)₃, La₂(CO₃)₃ or combinations thereof.

In yet other embodiments, a nanowire may serve as a support for anothernanowire. For example, a nanowire may be comprised of non-catalyticmetal elements and adhered to or incorporated within the supportnanowire is a catalytic nanowire. For example, in some embodiments, thesupport nanowires are comprised of SiO₂, MgO, CaO, SrO, TiO₂, ZrO₂,Al₂O₃, ZnO MgCO₃, CaCO₃, SrCO₃ or combinations thereof. Preparation ofnanowire supported nanowire catalysts (i.e., core/shell nanowires) isdiscussed in more detail below. The optimum amount of nanowire presenton the support depends, inter alia, on the catalytic activity of thenanowire. In some embodiments, the amount of nanowire present on thesupport ranges from 1 to 100 parts by weight nanowires per 100 parts byweight of support or from 10 to 50 parts by weight nanowires per 100parts by weight of support. In other embodiments, the amount of nanowirepresent on the support ranges from 100-200 parts of nanowires per 100parts by weight of support, or 200-500 parts of nanowires per 100 partsby weight of support, or 500-1000 parts of nanowires per 100 parts byweight of support. Typically, heterogeneous catalysts are used either intheir pure form or blended with inert materials, such as silica,alumina, etc. The blending with inert materials is used in order toreduce and/or control large temperature non-uniformities within thereactor bed often observed in the case of strongly exothermic (orendothermic) reactions. In the case of complex multistep reactions, suchas the reaction to convert methane into ethylene (OCM), typical blendingmaterials can selectively slow down or quench one or more of thereactions of the system and promote unwanted side reactions. Forexample, in the case of the oxidative coupling of methane, silica andalumina can quench the methyl radicals and thus prevent the formation ofethane. In certain aspects, the present disclosure provides a catalyticmaterial which solves these problems typically associated with catalystsupport material. Accordingly, in certain embodiments the catalyticactivity of the catalytic material can be tuned by blending two or morecatalysts and/or catalyst support materials. The blended catalyticmaterial may comprise a catalytic nanowire as described herein and abulk catalyst material and/or inert support material.

The blended catalytic materials comprise metal oxides, hydroxides,oxy-hydroxides, carbonates, oxalates of the groups 1-16, lanthanides,actinides or combinations thereof. For example, the blended catalyticmaterials may comprise a plurality of inorganic catalyticpolycrystalline nanowires, as disclosed herein, and any one or more ofstraight nanowires, nanoparticles, bulk materials and inert supportmaterials. Methods for preparing such other materials (e.g., straightnanowires) are known in the art and described in co-pending U.S.application Ser. No. 13/115,082, which application is herebyincorporated by reference in its entirety. Bulk materials are defined asany material in which no attempt to control the size and/or morphologywas performed during its synthesis. The catalytic materials may beundoped or may be doped with any of the dopants described herein.

In one embodiment, the catalyst blend comprises at least one type 1component and at least one type 2 component. Type 1 components comprisecatalysts having a high OCM activity at moderately low temperatures andtype 2 components comprise catalysts having limited or no OCM activityat these moderately low temperatures, but are OCM active at highertemperatures. For example, in some embodiments the type 1 component is acatalyst (e.g., nanowire) having high OCM activity at moderately lowtemperatures. For example, the type 1 component may comprise a C2 yieldof greater than 5% or greater than 10% at temperatures less than 800°C., less than 700° C. or less than 600° C. The type 2 component maycomprise a C2 yield less than 0.1%, less than 1% or less than 5% attemperatures less than 800° C., less than 700° C. or less than 600° C.The type 2 component may comprise a C2 yield of greater than 0.1%,greater than 1%, greater than 5% or greater than 10% at temperaturesgreater than 800° C., greater than 700° C. or greater than 600° C.Typical type 1 components include nanowires, for example polycrystallinenanowires as described herein, while typical type 2 components includebulk OCM catalysts and nanowire catalysts which only have good OCMactivity at higher temperatures, for example greater than 800° C.Examples of type 2 components may include catalysts comprising MgO. Thecatalyst blend may further comprise inert support materials as describedabove (e.g., silica, alumina, silicon carbide, etc.).

In certain embodiments, the type 2 component acts as diluent in the sameway an inert material does and thus helps reduce and/or control hotspots in the catalyst bed caused by the exothermic nature of the OCMreaction. However, because the type 2 component is an OCM catalyst,albeit not a particularly active one, it may prevent the occurrence ofundesired side reactions, e.g. methyl radical quenching. Additionally,controlling the hotspots has the beneficial effect of extending thelifetime of the catalyst.

For example, it has been found that diluting active lanthanide oxide OCMcatalysts (e.g., nanowires) with as much as a 10:1 ratio of MgO, whichby itself is not an active OCM catalyst at the temperature which thelanthanide oxide operates, is a good way to minimize “hot spots” in thereactor catalyst bed, while maintaining the selectivity and yieldperformance of the catalyst. On the other hand, doing the same dilutionwith quartz SiO₂ is not effective because it appears to quench themethyl radicals which serve to lower the selectivity to C2s.

In yet another embodiment, the type 2 components are good oxidativedehydrogenation (ODH) catalysts at the same temperature that the type 1components are good OCM catalysts. In this embodiment, theethylene/ethane ratio of the resulting gas mixture can be tuned in favorof higher ethylene. In another embodiment, the type 2 components are notonly good ODH catalysts at the same temperature the type 1 componentsare good OCM catalysts, but also have limited to moderate OCM activityat these temperatures.

In related embodiments, the catalytic performance of the catalyticmaterial is tuned by selecting specific type 1 and type 2 components ofa catalyst blend. In another embodiment, the catalytic performance istuned by adjusting the ratio of the type 1 and type 2 components in thecatalytic material. For example, the type 1 catalyst may be a catalystfor a specific step in the catalytic reaction, while the type 2 catalystmay be specific for a different step in the catalytic reaction. Forexample, the type 1 catalyst may be optimized for formation of methylradicals and the type 2 catalyst may be optimized for formation ofethane or ethylene.

In other embodiments, the catalytic material comprises at least twodifferent components (component 1, component 2, component 3, etc.). Thedifferent components may comprise different morphologies, e.g.nanowires, nanoparticles, bulk, etc. The different components in thecatalyst material can be, but not necessarily, of the same chemicalcomposition and the only difference is in the morphology and/or the sizeof the particles. This difference in morphology and particle size mayresult in a difference in reactivity at a specific temperature.Additionally, the difference in morphology and particle size of thecatalytic material components is advantageous for creating a veryintimate blending, e.g. very dense packing of the catalysts particles,which can have a beneficial effect on catalyst performance. Also, thedifference in morphology and particle size of the blend components wouldallow for control and tuning of the macro-pore distribution in thereactor bed and thus its catalytic efficiency. An additional level ofmicro-pore tuning can be attained by blending catalysts with differentchemical composition and different morphology and/or particle size. Theproximity effect would be advantageous for the reaction selectivity.

Accordingly, in one embodiment the present disclosure provides the useof a catalytic material comprising a first catalytic nanowire and a bulkcatalyst and/or a second catalytic nanowire in a catalytic reaction, forexample the catalytic reaction may be OCM or ODH. In other embodiments,the first catalytic nanowire and the bulk catalyst and/or secondcatalytic nanowire are each catalytic with respect to the same reaction,and in other examples the first catalytic nanowire and the bulk catalystand/or second catalytic nanowire have the same chemical composition.

In some specific embodiments of the foregoing, the catalytic materialcomprises a first catalytic nanowire and a second catalytic nanowire.Each nanowire can have completely different chemical compositions orthey may have the same base composition and differ only by the dopingelements. In other embodiments, each nanowire can have the same or adifferent morphology. For example, each nanowire can differ by thenanowire size (length and/or aspect ratio), by ratio of actual/effectivelength, by chemical composition or any combination thereof. Furthermore,the first and second nanowires may each be catalytic with respect to thesame reaction but may have different activity. Alternatively, eachnanowire may catalyze different reactions.

In a related embodiment, the catalytic material comprises a firstcatalytic nanowire and a bulk catalyst. The first nanowire and the bulkcatalyst can have completely different chemical compositions or they mayhave the same base composition and differ only by the doping elements.Furthermore, the first nanowire and the bulk catalyst may each becatalytic with resepect to the same reaction but may have differentactivity. Alternatively, the first nanowire and the bulk catalyst maycatalyze different reactions.

In yet other embodiments of the foregoing, the catalytic nanowire has acatalytic activity in the catalytic reaction, which is greater than acatalytic activity of the bulk catalyst in the catalytic reaction at thesame temperature. In still other embodiments, the catalytic activity ofthe bulk catalyst in the catalytic reaction increases with increasingtemperature.

OCM catalysts may be prone to hotspots due to the very exothermic natureof the OCM reaction. Diluting such catalysts helps to manage thehotspots. However, the diluent needs to be carefully chosen so that theoverall performance of the catalyst is not degraded. Silicon carbide forexample can be used as a diluent with little impact on the OCMselectivity of the blended catalytic material whereas using silica as adiluent significantly reduces OCM selectivity. The good heatconductivity of SiC is also beneficial in minimizing hot spots. As notedabove, use of a catalyst diluents or support material that is itself OCMactive has significant advantages over more traditional diluents such assilica and alumina, which can quench methyl radicals and thus reduce theOCM performance of the catalyst. An OCM active diluent is not expectedto have any adverse impact on the generation and lifetime of methylradicals and thus the dilution should not have any adverse impact on thecatalyst performance. Thus embodiments of the invention include catalystcompositions comprising an OCM catalyst (e.g., any of the disclosednanowire catalysts) in combination with a diluent or support materialthat is also OCM active. Methods for use of the same in an OCM reactionare also provided.

In some embodiments, the above diluent comprises alkaline earth metalcompounds, for example alkaline metal oxides, carbonates, sulfates orphosphates. Examples of diluents useful in various embodiments include,but are not limited to, MgO, MgCO₃, MgSO₄, Mg₃(PO₄)₂, MgAl₂O₄, CaO,CaCO₃, CaSO₄, Ca₃(PO₄)₂, CaAl₂O₄, SrO, SrCO₃, SrSO₄, Sr₃(PO₄)₂, SrAl₂O₄,BaO, BaCO₃, BaSO₄, Ba₃(PO₄)₂, BaAl₂O₄ and the like. Most of thesecompounds are very cheap, especially MgO, CaO, MgCO₃, CaCO₃, SrO, SrCO₃and thus very attractive for use as diluents from an economic point ofview. Additionally, the magnesium, calcium and strontium compounds areenvironmentally friendly too. Accordingly, an embodiment of theinvention provides a catalytic material comprising a catalytic nanowirein combination with a diluent selected from one or more of MgO, MgCO₃,MgSO₄, Mg₃(PO₄)₂, CaO, CaCO₃, CaSO₄, Ca₃(PO₄)₂, SrO, SrCO₃, SrSO₄,Sr₃(PO₄)₂, BaO, BaCO₃, BaSO₄, Ba₃(PO₄)₂. In some specific embodimentsthe diluents is MgO, CaO, SrO, MgCO₃, CaCO₃, SrCO₃ or combinationthereof. Methods for use of the foregoing catalytic materials in an OCMreaction are also provided. The methods comprise converting methane toethane and or ethylene in the presence of the catalytic materials.

The above diluents and supports may be employed in any number ofmethods. For example, in some embodiments a support (e.g., MgO, CaO,CaCO₃, SrCO₃) may be used in the form of a pellet or monolith (e.g.,honeycomb) structure, and the nanowire catalysts may be impregnated orsupported thereon. In other embodiments, a core/shell arrangement isprovided and the support material may form part of the core or shell.For example, a core of MgO, CaO, CaCO₃ or SrCO₃ may be coated with ashell of any of the disclosed nanowire compositions.

In some embodiments, the diluent has a morphology selected from bulk(e.g. commercial grade), nano (nanowires, nanorods, nanoparticles, etc.)or combinations thereof.

In some embodiments, the diluent has none to moderate catalytic activityat the temperature the OCM catalyst is operated. In some otherembodiments, the diluent has moderate to large catalytic activity at atemperature higher than the temperature the OCM catalyst is operated. Inyet some other embodiments, the diluent has none to moderate catalyticactivity at the temperature the OCM catalyst is operated and moderate tolarge catalytic activity at temperatures higher than the temperature theOCM catalyst is operated. Typical temperatures for operating an OCMreaction according to the present disclosure are 800° C. or lower, 750°C. or lower, 700° C. or lower, 650° C. or lower, 600° C. or lower and550° C. or lower.

For example, CaCO₃ is a relatively good OCM catalyst at T>750° C. (50%selectivity, >20% conversion) but has essentially no activity below 700°C. Experiments performed in support of the present invention showed thatdilution of Nd₂O₃ straight nanowires with CaCO₃ or SrCO₃ (bulk) showedno degradation of OCM performance and, in some cases, even betterperformance than the neat catalyst.

In some embodiments, the diluent portion in the catalyst/diluent mixtureis 0.01%, 10%, 30%, 50%, 70%, 90% or 99.99% (weight percent) or anyother value between 0.01% and 99.9%. In some embodiments, the dilutionis performed with the OCM catalyst ready to go, e.g. after calcination.In some other embodiments, the dilution is performed prior to the finalcalcination of the catalyst, i.e. the catalyst and the diluent arecalcined together. In yet some other embodiments, the dilution can bedone during the synthesis as well, so that, for example, a mixed oxideis formed.

In some embodiments, the catalyst/diluent mixture comprises more thanone catalyst and/or more than one diluent. In some other embodiments,the catalyst/diluent mixture is pelletized and sized, or made intoshaped extrudates or deposited on a monolith or foam, or is used as itis. Methods of the invention include taking advantage of the veryexothermic nature of OCM by diluting the catalyst with another catalystthat is (almost) inactive in the OCM reaction at the operatingtemperature of the first catalyst but active at higher temperature. Inthese methods, the heat generated by the hotspots of the first catalystwill provide the necessary heat for the second catalyst to becomeactive.

For ease of illustration, the above description of catalytic materialsoften refers to OCM; however, such catalytic materials find utility inother catalytic reactions including but not limited to: oxidativedehydrogenation (ODH) of alkanes to their corresponding alkenes,selective oxidation of alkanes and alkenes and alkynes, oxidation of co,dry reforming of methane, selective oxidation of aromatics,Fischer-Tropsch, combustion of hydrocarbons, etc.

4. Preparation of Catalytic Materials

The catalytic materials can be prepared according to any number ofmethods known in the art. For example, the catalytic materials can beprepared after preparation of the individual components by mixing theindividual components in their dry form, e.g. blend of powders, andoptionally, ball milling can be used to reduce particle size and/orincrease mixing. Each component can be added together or one after theother to form layered particles. Alternatively, the individualcomponents can be mixed prior to calcination, after calcination or bymixing already calcined components with uncalcined components. Thecatalytic materials may also be prepared by mixing the individualcomponents in their dry form and optionally pressing them together intoa “pill” followed by calcination to above 400° C.

In other examples, the catalytic materials are prepared by mixing theindividual components with one or more solvents into a suspension orslurry, and optional mixing and/or ball milling can be used to maximizeuniformity and reduce particle size. Examples of slurry solvents usefulin this context include, but are not limited to: water, alcohols,ethers, carboxylic acids, ketones, esters, amides, aldehydes, amines,alkanes, alkenes, alkynes, aromatics, etc. In other embodiments, theindividual components are deposited on a supporting material such assilica, alumina, magnesia, activated carbon, and the like, or by mixingthe individual components using a fluidized bed granulator. Combinationsof any of the above methods may also be used.

The catalytic materials may optionally comprise a dopant as described inmore detail below. In this respect, doping material(s) may be addedduring preparation of the individual components, after preparation ofthe individual components but before drying of the same, after thedrying step but before calcinations or after calcination. If more thanone doping material is used, each dopant can be added together or oneafter the other to form layers of dopants.

Doping material(s) may also be added as dry components and optionallyball milling can be used to increase mixing. In other embodiments,doping material(s) are added as a liquid (e.g. solution, suspension,slurry, etc.) to the dry individual catalyst components or to theblended catalytic material. The amount of liquid may optionally beadjusted for optimum wetting of the catalyst, which can result inoptimum coverage of catalyst particles by doping material. Mixing and/orball milling can also be used to maximize doping coverage and uniformdistribution. Alternatively, doping material(s) are added as a liquid(e.g. solution, suspension, slurry, etc.) to a suspension or slurry ofthe catalyst in a solvent. Mixing and/or ball milling can be used tomaximize doping coverage and uniform distribution. Incorporation ofdopants can also be achieved using any of the methods describedelsewhere herein.

As noted below, an optional calcination step usually follows an optionaldrying step at T<200 C (typically 60-120 C) in a regular oven or in avacuum oven. Calcination may be performed on the individual componentsof the catalytic material or on the blended catalytic material.Calcination is generally performed in an oven/furnace at a temperaturehigher than the minimum temperature at which at least one of thecomponents decomposes or undergoes a phase transformation and can beperformed in inert atmosphere (e.g. N₂, Ar, He, etc.), oxidizingatmosphere (air, O₂, etc.) or reducing atmosphere (H₂, H₂/N₂, H₂/Ar,etc.). The atmosphere may be a static atmosphere or a gas flow and maybe performed at ambient pressure, at p<1 atm, in vacuum or at p>1 atm.High pressure treatment (at any temperature) may also be used to inducephase transformation including amorphous to crystalline. Calcinationsmay also be performed using microwave heating.

Calcination is generally performed in any combination of stepscomprising ramp up, dwell and ramp down. For example, ramp to 500° C.,dwell at 500° C. for 5 h, ramp down to RT. Another example includes rampto 100° C., dwell at 100° C. for 2 h, ramp to 300° C., dwell at 300° C.for 4 h, ramp to 550° C., dwell at 550° C. for 4 h, ramp down to RT.Calcination conditions (pressure, atmosphere type, etc.) can be changedduring the calcination. In some embodiments, calcination is performedbefore preparation of the blended catalytic material (i.e., individualcomponents are calcined), after preparation of the blended catalyticmaterial but before doping, after doping of the individual components orblended catalytic material. Calcination may also be performed multipletimes, e.g. after catalyst preparation and after doping.

The catalytic materials may be incorporated into a reactor bed forperforming any number of catalytic reactions (e.g., OCM, ODH and thelike). Accordingly, in one embodiment the present disclosure provides acatalytic material as disclosed herein in contact with a reactor and/orin a reactor bed. For example, the reactor may be for performing an OCMreaction, may be a fixed bed reactor and may have a diameter greaterthan 1 inch. In this regard, the catalytic material may be packed neat(without diluents) or diluted with an inert material (e.g., sand,silica, alumina, etc.) The catalyst components may be packed uniformlyforming a homogeneous reactor bed.

The particle size of the individual components within a catalyticmaterial may also alter the catalytic activity, and other properties, ofthe same. Accordingly, in one embodiment, the catalyst is milled to atarget average particle size or the catalyst powder is sieved to selecta particular particle size. In some aspects, the catalyst powder may bepressed into pellets and the catalyst pellets can be optionally milledand or sieved to obtain the desired particle size distribution.

In some embodiments, the catalyst materials, alone or with bindersand/or diluents, can be configured into larger aggregate forms, such aspellets, extrudates, or other aggregations of catalyst particles. Forease of duscussion, such larger forms are generally referred to hereinas “pellets”. Such pellets may optionally include a binder and/orsupport material; however, the present inventors have surprisingly foundthat the disclosed nanowires are particularly suited to used in the formof a pellet without a binder and/or support material. Accordingly, oneembodiment of the disclosure provides a catalytic material in theabsence of a binder. In this regard, the morphology of the disclosednanowires (either bent or straight, etc.) is believed to contribute tothe nanowires' ability to be pressed into pellets without the need for abinder. Catalytic materials without binders are simpler, less complexand cheaper than corresponding materials with binders and thus offercertain advantages.

In some instances, catalytic materials may be prepared using a“sacrificial binder” or support. Because of their special properties,the nanowires allow for preparation of catalytic material forms (e.g.pellets) without the use of a binder. A “sacrificial” binder can be usedin order to create unique microporosity in pellets or extrudates. Afterremoving the sacrificial binder, the structural integrity of thecatalyst is ensured by the special binding properties of the nanowiresand the resulting catalytic material has unique microporosity as aresult of removing the binder. For example, in some embodiments acatalytic nanowire may be prepared with a binder and then the binderremoved by any number of techniques (e.g., combustion, calcinations,acid erosion, etc.). This method allows for design and preparation ofcatalytic materials having unique microporosity (i.e., the microporosityis a function of size, etc. of the sacrificial binder). The ability toprepare different forms (e.g., pellets) of the nanowires without the useof binder is not only useful for preparation of catalytic materials fromthe nanowires, but also allows the nanowires to be used as supportmaterials (or both catalytic and support material). Sacrificial bindersand techniques useful in this regard include sacrificial cellulosicfibers or other organic polymers that can be easily removed bycalcination, non-sacrificial binders and techniques useful in thisregard include, colloidal oxide binders such as Ludox Silica or Nyacolcolloidal zirconia that can also be added to strengthen the formedaggregate when needed. Sacrificial binders are added to increasemacro-porosity (pores larger than 20 nm diameter) of the catalyticmaterials. Accordingly, in some embodiments the catalytic materialscomprise pores greater than 20 nm in diameter, greater than 50 nm indiameter, greater than 75 nm in diameter, greater than 100 nm indiameter or greater than 150 nm in diameter.

Catalytic materials also include any of the disclosed nanowires disposedon or adhered to a solid support. For example, the nanowires may beadhered to the surface of a monolith support. As with the binder-lessmaterials discussed above, in these embodiments the nanowires may beadhered to the surface of the monolith in the absence of a binder due totheir unique morphology and packing properties. Monoliths includehoneycomb-type structures, foams and other catalytic support structuresderivable by one skilled in the art. In one embodiment, the support is ahoneycomb matrix formed from silicon carbide, and the support furthercomprises catalytic nanowires disposed on the surface.

As the OCM reaction is very exothermic, it can be desirable to reducethe rate of conversion per unit volume of reactor in order to avoid runaway temperature rise in the catalyst bed that can result in hot spotsaffecting performance and catalyst life. One way to reduce the OCMreaction rate per unit volume of reactor is to spread the activecatalyst onto an inert support with interconnected large pores as inceramic or metallic foams (including metal alloys having reducedreactivity with hydrocarbons under OCM reaction conditions) or havingarrays of channel as in honeycomb structured ceramic or metal assembly.

In one embodiment, a catalytic material comprising a catalytic nanowireas disclosed herein supported on a structured support is provided.Examples of such structure supports include, but are not limited to,metal foams, Silicon Carbide or Alumina foams, corrugated metal foilarranged to form channel arrays, extruded ceramic honeycomb, for exampleCordierite (available from Corning or NGK ceramics, USA), SiliconCarbide or Alumina.

Active catalyst loading on the structured support ranges from 1 to 500mg per ml of support component, for example from 5 to 100 mg per ml ofstructure support. Cell densities on honeycomb structured supportmaterials may range from 100 to 900 CPSI (cell per square inch), forexample 200 to 600 CPSI. Foam densities may range from 10 to 100 PPI(pore per inch), for example 20 to 60 PPI.

In other embodiments, the exotherm of the OCM reaction may be at leastpartially controlled by blending the active catalytic material withcatalytically inert material, and pressing or extruding the mixture intoshaped pellets or extrudates. In some embodiments, these mixed particlesmay then be loaded into a pack-bed reactor. The Extrudates or pelletscomprise between 30% to 70% pore volume with 5% to 50% active catalystweight fraction. Useful inert materials in this regard include, but arenot limited to MgO, CaO, Al₂O₃, SiC and cordierite.

In addition to reducing the potential for hot spots within the catalyticreactor, another advantage of using a structured ceramic with large porevolume as a catalytic support is reduced flow resistance at the same gashourly space velocity versus a pack-bed containing the same amount ofcatalyst.

Yet another advantage of using such supports is that the structuredsupport can be used to provide features difficult to obtain in apack-bed reactor. For example the support structure can improve mixingor enabling patterning of the active catalyst depositions through thereactor volume. Such patterning can consist of depositing multiplelayers of catalytic materials on the support in addition to the OCMactive component in order to affect transport to the catalyst orcombining catalytic functions as adding O2-ODH activity, CO2-OCMactivity or CO2-ODH activity to the system in addition to O2-OCM activematerial. Another patterning strategy can be to create bypass within thestructure catalyst essentially free of active catalyst to limit theoverall conversion within a given supported catalyst volume.

Yet another advantage is reduced heat capacity of the bed of thestructured catalyst over a pack bed a similar active catalyst loadingtherefore reducing startup time.

Nanowire shaped catalysts are particularly well suited for incorporationinto pellets or extrudates or deposition onto structured supports.Nanowire aggregates forming a mesh type structure can have good adhesiononto rough surfaces.

The mesh like structure can also provide improved cohesion in compositeceramic improving the mechanical properties of pellets or extrudatescontaining the nanowire shaped catalyst particles.

Alternatively, such nanowire on support or in pellet form approaches canbe used for other reactions besides OCM, such as ODH, dry methanereforming, FT, and all other catalytic reactions.

In yet another embodiment, the catalysts are packed in bands forming alayered reactor bed. Each layer is composed by either a catalyst of aparticular type, morphology or size or a particular blend of catalysts.In one embodiment, the catalysts blend may have better sinteringproperties, i.e. lower tendency to sinter, then a material in its pureform. Better sintering resistance is expected to increase the catalyst'slifetime and improve the mechanical properties of the reactor bed.

In yet other embodiments, the disclosure provides a catalytic materialcomprising one or more different catalysts. The catalysts may be ananowire as disclosed herein and a different catalyst for example a bulkcatalysts. Mixtures of two or more nanowire catalysts are alsocontemplated. The catalytic material may comprise a catalyst, forexample a nanowire catalyst, having good OCM activity and a catalysthaving good activity in the ODH reaction. Either one or both of thesecatalysts may be nanowires as disclosed herein.

On skilled in the art will recognize that various combinations oralternatives of the above methods are possible, and such variations arealso included within the scope of the present disclosure.

5. Dopants

In further embodiments, the disclosure provides nanowires comprising adopant (i.e., doped nanowires). As noted above, dopants or doping agentsare impurities added to or incorporated within a catalyst to optimizecatalytic performance (e.g., increase or decrease catalytic activity).As compared to the undoped catalyst, a doped catalyst may increase ordecrease the selectivity, conversion, and/or yield of a catalyticreaction. In one embodiment, nanowire dopants comprise one or more metalelements, semi-metal elements, non-metal elements or combinationsthereof. Although oxygen is included in the group of nonmetal elements,in certain embodiments oxygen is not considered a dopant. For example,certain embodiments are directed to nanowires comprising two, three oreven four or more dopants, and the dopants are non-oxygen dopants. Thusin these embodiments, a metal oxide nanowire is not considered to be ametal nanowire doped with oxygen. Analagously, in the case of mixedoxides (i.e., M1_(x)M2_(y)O_(z)), both the metal elements and oxygen areconsidered a part of the base catalyst (nanowire) and are not includedin the total number of dopants.

The dopant may be present in any form and may be derived from anysuitable source of the element (e.g., chlorides, bromides, iodides,nitrates, oxynitrates, oxyhalides, acetates, formates, hydroxides,carbonates, phosphates, sulfates, alkoxides, and the like.). In someembodiments, the nanowire dopant is in elemental form. In otherembodiments, the nanowire dopant is in reduced or oxidized form. Inother embodiments, the nanowire dopant comprises an oxide, hydroxide,carbonate, nitrate, acetate, sulfate, formate, oxynitrate, halide,oxyhalide or hydroxyhalide of a metal element, semi-metal element ornon-metal element or combinations thereof.

In one embodiment, the nanowires comprise one or more metal elementsselected from Groups 1-7, lanthanides, actinides or combinations thereofin the form of an oxide and further comprise one or more dopants,wherein the one or more dopants comprise metal elements, semi-metalelements, non-metal elements or combinations thereof. In anotherembodiment, the nanowires comprise one or more metal elements selectedfrom group 1 in the form of an oxide and further comprise one or moredopants, wherein the one or more dopants comprise metal elements,semi-metal elements, non-metal elements or combinations thereof. Inanother embodiment, the nanowires comprise one or more metal elementsselected from group 2 in the form of an oxide and further comprise oneor more dopants, wherein the one or more dopants comprise metalelements, semi-metal elements, non-metal elements or combinationsthereof. In another embodiment, the nanowires comprise one or more metalelements selected from group 3 in the form of an oxide and furthercomprise one or more dopants, wherein the one or more dopants comprisemetal elements, semi-metal elements, non-metal elements or combinationsthereof. In another embodiment, the nanowires comprise one or more metalelements selected from group 4 in the form of an oxide and furthercomprise one or more dopants, wherein the one or more dopants comprisemetal elements, semi-metal elements, non-metal elements or combinationsthereof. In another embodiment, the nanowires comprise one or more metalelements selected from group 5 in the form of an oxide and furthercomprise one or more dopants, wherein the one or more dopants comprisemetal elements, semi-metal elements, non-metal elements or combinationsthereof. In another embodiment, the nanowires comprise one or more metalelements selected from group 6 in the form of an oxide and furthercomprise one or more dopants, wherein the one or more dopants comprisemetal elements, semi-metal elements, non-metal elements or combinationsthereof. In another embodiment, the nanowires comprise one or more metalelements selected from group 7 in the form of an oxide and furthercomprise one or more dopants, wherein the one or more dopants comprisemetal elements, semi-metal elements, non-metal elements or combinationsthereof. In another embodiment, the nanowires comprise one or more metalelements selected from lanthanides in the form of an oxide and furthercomprise one or more dopants, wherein the one or more dopants comprisemetal elements, semi-metal elements, non-metal elements or combinationsthereof. In another embodiment, the nanowires comprise one or more metalelements selected from actinides in the form of an oxide and furthercomprise one or more dopants, wherein the one or more dopants comprisemetal elements, semi-metal elements, non-metal elements or combinationsthereof.

For example, in one embodiment, the nanowire dopant comprises Li,Li₂CO₃, LiOH, Li₂O, LiCl, LiNO₃, Na, Na₂CO₃, NaOH, Na₂O, NaCl, NaNO₃, K,K₂CO₃, KOH, K₂O, KCl, KNO₃, Rb, Rb₂CO₃, RbOH, Rb₂O, RbCl, RbNO₃, Cs,Cs₂CO₃, CsOH, Cs₂O, CsCl, CsNO₃, Mg, MgCO₃, Mg(OH)₂, MgO, MgCl₂,Mg(NO₃)₂, Ca, CaO, CaCO₃, Ca(OH)₂, CaCl₂, Ca(NO₃)₂, Sr, SrO, SrCO₃,Sr(OH)₂, SrCl₂, Sr(NO₃)₂, Ba, BaO, BaCO₃, Ba(OH)₂, BaCl₂, Ba(NO₃)₂, La,La₂O₃, La₂(CO₃)₃, La(OH)₃, LaCl₃, La(NO₃)₂, Nd, Nd₂O₃, Nd₂(CO₃)₃,Nd(OH)₃, NdCl₃, Nd(NO₃)₂, Sm, Sm₂O₃, Sm₂(CO₃)₃, Sm(OH)₃, SmCl₃,Sm(NO₃)₂, Eu, Eu₂O₃, Eu₂(CO₃)₃, Eu(OH)₃, EuCl₃, Eu(NO₃)₂, Gd, Gd₂O₃,Gd₂(CO₃)₃, Gd(OH)₃, GdCl₃, Gd(NO₃)₂, Ce, Ce(OH)₄, CeO₂, Ce₂O₃, Ce(CO₃)₂,CeCl₄, Ce(NO₃)₂, Th, ThO₂, ThCl₄, Th(OH)₄, Zr, ZrO₂, ZrCl₄, Zr(OH)₄,ZrOCl₂, Zr(CO₃)2, ZrOCO₃, ZrO(NO₃)₂, P, phosphorous oxides, phosphorouschlorides, phosphorous carbonates, Ni, nickel oxides, nickel chlorides,nickel carbonates, nickel hydroxides, Nb, niobium oxides, niobiumchlorides, niobium carbonates, niobium hydroxides, Au, gold oxides, goldchlorides, gold carbonates, gold hydroxides, Mo, molybdenum oxides,molybdenum chlorides, molybdenum carbonates, molybdenum hydroxides,tungsten chlorides, tungsten carbonates, tungsten hydroxides, Cr,chromium oxides, chromium chlorides, chromium hydroxides, Mn, manganeseoxides, manganese chlorides, manganese hydroxides, Zn, ZnO, ZnCl₂,Zn(OH)₂, B, borates, BCl₃, N, nitrogen oxides, nitrates, La, Ce, Pr, Nd,Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, In, Y, Sc, Al, Cu, Cs, Ga,Hf, Fe, Ru, Rh, Be, Co, Sb, V, Ag, Te, Pd, Tb, Ir, Rb or combinationsthereof. In other embodiments, the nanowire dopant comprises Li, Na, K,Rb, Cs, Mg, Ca, Sr, Eu, In, Nd, Sm, Ce, Gd, Tb, Er, Tm, Yb, Y, Sc orcombinations thereof.

In other embodiments, the nanowire dopant comprises Li, Li₂O, Na, Na₂O,K, K₂O, Mg, MgO, Ca, CaO, Sr, SrO, Ba, BaO, La, La₂O₃, Ce, CeO₂, Ce₂O₃,Th, ThO₂, Zr, ZrO₂, P, phosphorous oxides, Ni, nickel oxides, Nb,niobium oxides, Au, gold oxides, Mo, molybdenum oxides, Cr, chromiumoxides, Mn, manganese oxides, Zn, ZnO, B, borates, N, nitrogen oxides orcombinations thereof. In other embodiments, the nanowire dopantcomprises Li, Na, K, Mg, Ca, Sr, Ba, La, Ce, Th, Zr, P, Ni, Nb, Au, Mo,Cr, Mn, Zn, B, N or combinations thereof. In other embodiments, thenanowire dopant comprises Li₂O, Na₂O, K₂O, MgO, CaO, SrO, BaO, La₂O₃,CeO₂, Ce₂O₃, ThO₂, ZrO₂, phosphorous oxides, nickel oxides, niobiumoxides, gold oxides, molybdenum oxides, chromium oxides, manganeseoxides, ZnO, borates, nitrogen oxides or combinations thereof. Infurther embodiments, the dopant comprises Sr or Li. In other specificembodiments, the nanowire dopant comprises La, Ce, Pr, Nd, Pm, Sm, Eu,Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, In, Y, Sc or combinations thereof. Inother specific embodiments, the nanowire dopant comprises Li, Na, K, Mg,Ca, Ba, Sr, Eu, Sm, Co or Mn.

In certain embodiments, the dopant comprises an element from group 1. Insome embodiments, the dopant comprises lithium. In some embodiments, thedopant comprises sodium. In some embodiments, the dopant comprisespotassium. In some embodiments, the dopant comprises rubidium. In someembodiments, the dopant comprises caesium.

In some embodiments the nanowires comprise a lanthanide element and aredoped with a dopant from group 1, group 2, or combinations thereof. Forexample, in some embodiments, the nanowires comprise a lanthanideelement and are doped with lithium. In other embodiments, the nanowirescomprise a lanthanide element and are doped with sodium. In otherembodiments, the nanowires comprise a lanthanide element and are dopedwith potassium. In other embodiments, the nanowires comprise alanthanide element and are doped with rubidium. In other embodiments,the nanowires comprise a lanthanide element and are doped with caesium.In other embodiments, the nanowires comprise a lanthanide element andare doped with beryllium. In other embodiments, the nanowires comprise alanthanide element and are doped with magnesium. In other embodiments,the nanowires comprise a lanthanide element and are doped with calcium.In other embodiments, the nanowires comprise a lanthanide element andare doped with strontium. In other embodiments, the nanowires comprise alanthanide element and are doped with barium.

In some embodiments the nanowires comprise a transition metal tungstate(e.g., Mn/W and the like) and are doped with a dopant from group 1,group 2, or combinations thereof. For example, in some embodiments, thenanowires comprise a transition metal tungstate and are doped withlithium. In other embodiments, the nanowires comprise a transition metaltungstate and are doped with sodium. In other embodiments, the nanowirescomprise a transition metal tungstate and are doped with potassium. Inother embodiments, the nanowires comprise a transition metal tungstateand are doped with rubidium. In other embodiments, the nanowirescomprise a transition metal tungstate and are doped with caesium. Inother embodiments, the nanowires comprise a transition metal tungstateand are doped with beryllium. In other embodiments, the nanowirescomprise a transition metal tungstate and are doped with magnesium. Inother embodiments, the nanowires comprise a transition metal tungstateand are doped with calcium. In other embodiments, the nanowires comprisea transition metal tungstate and are doped with strontium. In otherembodiments, the nanowires comprises a transition metal tungstate andare doped with barium.

In some embodiments the nanowires comprise Mn/Mg/O and are doped with adopant from group 1, group 2, group 7, group 8, group 9 or group 10 orcombinations thereof. For example, in some embodiments, the nanowirescomprise Mn/Mg/O and are doped with lithium. In other embodiments, thenanowires comprise Mn/Mg/O and are doped with sodium. In otherembodiments, the nanowires comprise Mn/Mg/O and are doped withpotassium. In other embodiments, the nanowires comprise Mn/Mg/O and aredoped with rubidium. In other embodiments, the nanowires compriseMn/Mg/O and are doped with caesium. In other embodiments, the nanowirescomprise Mn/Mg/O and are doped with beryllium. In other embodiments, thenanowires comprise Mn/Mg/O and are doped with magnesium. In otherembodiments, the nanowires comprise Mn/Mg/O and are doped with calcium.In other embodiments, the nanowires comprise Mn/Mg/O and are doped withstrontium. In other embodiments, the nanowires comprise Mn/Mg/O and aredoped with barium.

In yet some other embodiments, the nanowires comprise Mn/Mg/O and aredoped with manganese. In other embodiments, the nanowires compriseMn/Mg/O and are doped with technetium. In other embodiments, thenanowires comprise Mn/Mg/O and are doped with rhenium. In otherembodiments, the nanowires comprise Mn/Mg/O and are doped with iron. Inother embodiments, the nanowires comprise Mn/Mg/O and are doped withruthenium. In other embodiments, the nanowires comprise Mn/Mg/O and aredoped with osmium. In other embodiments, the nanowires comprise Mn/Mg/Oand are doped with cobalt. In other embodiments, the nanowires compriseMn/Mg/O and are doped with rhodium. In other embodiments, the nanowirescomprise Mn/Mg/O and are doped with iridium. In other embodiments, thenanowires comprise Mn/Mg/O and are doped with nickel. In otherembodiments, the nanowires comprise Mn/Mg/O and are doped withpalladium. In other embodiments, the nanowires comprise Mn/Mg/O and aredoped with platinum.

As noted above, the present inventors have determined that certainnanowire catalysts comprising rare earth elements(e.g., rare earthoxides) are useful as catalysts in a number of reactions, for examplethe OCM reaction. In certain embodiments the rare earth element is La,Nd, Eu, Sm, Yb, Gd or Y. In some embodiments, the rare earth element isLa. In other embodiments, the rare earth element is Nd. In otherembodiments, the rare earth element is Eu. In other embodiments, therare earth element is Sm. In other embodiments, the rare earth elementis Yb. In other embodiments, the rare earth element is Gd. In otherembodiments, the rare earth element is Y.

In certain embodiments of the nanowire catalysts comprising rare earthelements, the catalyst may further comprise a dopant selected fromalkaline earth (Group 2) elements. For example, in some embodiments thedopant is selected from Be, Mg, Ca, Sr and Ba. In other embodiments, thedopant is Be. In other embodiments, the dopant is Ca. In otherembodiments, the dopant is Sr. In other embodiments, the dopant is Ba.

In some embodiments, these rare earth compositions comprise La₂O₃,Nd₂O₃, Yb₂O₃, Eu₂O₃, Sm₂O₃, Y₂O₃, Ce₂O₃, Pr₂O₃, Ln1_(4-x)Ln2_(x)O₆,La_(4-x)Ln1_(x)O₆, La_(4-x)Nd_(x)O₆, La₃NdO₆, LaNd₃O₆,La_(1.5)Nd_(2.5)O₆, La_(2.5)Nd_(1.5)O₆, La_(3.2)Nd_(0.8)O₆,La_(3.5)Nd_(0.5)O₆, La_(3.8)Nd_(0.2)O₆, Y—La, Zr—La, Pr—La or Ce—La orcombinations thereof, wherein Ln1 and Ln2 are each independently alanthanide element, wherein Ln1 and Ln2 are not the same and x is anumber ranging from greater than 0 to less than 4.

Further, Applicants have discovered that certain doping combinations,when combined with the above rare earth compositions, serve to enhancethe catalytic activity of the nanowires in certain catalytic reactions,for example OCM. The dopants may be present in various levels (e.g.,w/w), and the nanowires may be prepared by any number of methods.Various aspects of the above nanowires are provided in the followingparagraphs and in Tables 9-12.

In certain embodiments, the above rare earth compositions comprise astrontium dopant and at least one more additional dopant selected fromgroup 1, 4-6, 13 and lanthanides. For example, in some embodiments theadditional dopant is Hf, K, Zr, Ce, Tb, Pr, W, Rb, Ta, B or combinationsthereof. In other embodiments, the dopant comprises Sr/Hf, Sr/Hf/K,Sr/Zr, Sr/Zr/K, Sr/Ce, Sr/Ce/K, Sr/Tb, Sr/Tb/K, Sr/Pr, Sr/Pr/K, Sr/W,Sr/Hf/Rb, Sr/Ta or Sr/B. In some other embodiments, the foregoing rareearth nanowires comprise La₂O₃ or La₃NdO₆.

In other embodiments, the nanowire catalysts comprise a rare earth oxideand dopants selected from at least one of the following combinationsEu/Na, Sr/Na, Mg/Na, Sr/W, K/La, K/Na, Li/Cs, Li/Na, Zn/K, Li/K, Rb/Hf,Ca/Cs, Hf/Bi, Sr/Sn, Sr/W, Sr/Nb, Zr/W, Y/W, Na/W, Bi/W, Bi/Cs, Bi/Ca,Bi/Sn, Bi/Sb, Ge/Hf, Hf/Sm, Sb/Ag, Sb/Bi, Sb/Au, Sb/Sm, Sb/Sr, Sb/W,Sb/Hf, Sb/Yb, Sb/Sn, Yb/Au, Yb/Ta, Yb/W, Yb/Sr, Yb/Pb, Yb/W, Yb/Ag,Au/Sr, W/Ge, Ta/Hf, W/Au, Ca/W, Au/Re, Sm/Li, La/K, Zn/Cs, Zr/Cs, Ca/Ce,Li/Sr, Cs/Zn, Dy/K, La/Mg, In/Sr, Sr/Cs, Ga/Cs, Lu/Fe, Sr/Tm, La/Dy,Mg/K, Zr/K, Li/Cs, Sm/Cs, In/K, Lu/Tl, Pr/Zn, Lu/Nb, Na/Pt, Na/Ce,Ba/Ta, Cu/Sn, Ag/Au, Al/Bi, Al/Mo, Al/Nb, Au/Pt, Ga/Bi, Mg/W, Pb/Au,Sn/Mg, Zn/Bi, Gd/Ho, Zr/Bi, Ho/Sr, Ca/Sr, Sr/Pb and Sr/Hf.

In still other embodiments, the nanowire catalysts comprise a rare earthoxide and dopants selected from at least one of the followingcombinations La/Nd, La/Sm, La/Ce, La/Sr, Eu/Na, Eu/Gd, Ca/Na, Eu/Sm,Eu/Sr, Mg/Sr, Ce/Mg, Gd/Sm, Sr/W, Sr/Ta, Au/Re, Au/Pb, Bi/Hf, Sr/Sn orMg/N, Ca/S, Rb/S, Sr/Nd, Eu/Y, Mg/Nd, Sr/Na, Nd/Mg, La/Mg, Yb/S, Mg/Na,Sr/W, K/La, K/Na, Li/Cs, Li/Na, Zn/K, Li/K, Rb/Hf, Ca/Cs, Hf/Bi, Sr/Sn,Sr/W, Sr/Nb, Zr/W, Y/W, Na/W, Bi/W, Bi/Cs, Bi/Ca, Bi/Sn, Bi/Sb, Ge/Hf,Hf/Sm, Sb/Ag, Sb/Bi, Sb/Au, Sb/Sm, Sb/Sr, Sb/W, Sb/Hf, Sb/Yb, Sb/Sn,Yb/Au, Yb/Ta, Yb/W, Yb/Sr, Yb/Pb, Yb/W, Yb/Ag, Au/Sr, W/Ge, Ta/Hf, W/Au,Ca/W, Au/Re, Sm/Li, La/K, Zn/Cs, Zr/Cs, Ca/Ce, Li/Sr, Cs/Zn, Dy/K,La/Mg, In/Sr, Sr/Cs, Ga/Cs, Lu/Fe, Sr/Tm, La/Dy, Mg/K, Zr/K, Li/Cs,Sm/Cs, In/K, Lu/Tl, Pr/Zn, Lu/Nb, Na/Pt, Na/Ce, Ba/Ta, Cu/Sn, Ag/Au,Al/Bi, Al/Mo, Al/Nb, Au/Pt, Ga/Bi, Mg/W, Pb/Au, Sn/Mg, Zn/Bi, Gd/Ho,Zr/Bi, Ho/Sr, Ca/Sr, Sr/Pb and Sr/Hf.

In other embodiments of the foregoing rare earth oxide nanowirecatalysts, the nanowire catalysts comprise a combination of two dopingelements. In some embodiments, the combination of two doping elements isLa/Nd. In other embodiments, the combination of two doping elements isLa/Sm. In other embodiments, the combination of two doping elements isLa/Ce. In other embodiments, the combination of two doping elements isLa/Sr. In other embodiments, the combination of two doping elements isEu/Na. In other embodiments, the combination of two doping elements isEu/Gd. In other embodiments, the combination of two doping elements isCa/Na. In other embodiments, the combination of two doping elements isEu/Sm. In other embodiments, the combination of two doping elements isEu/Sr. In other embodiments, the combination of two doping elements isMg/Sr. In other embodiments, the combination of two doping elements isCe/Mg. In other embodiments, the combination of two doping elements isGd/Sm. In other embodiments, the combination of two doping elements isSr/W. In other embodiments, the combination of two doping elements isSr/Ta. In other embodiments, the combination of two doping elements isAu/Re. In other embodiments, the combination of two doping elements isAu/Pb. In other embodiments, the combination of two doping elements isBi/Hf. In other embodiments, the combination of two doping elements isSr/Sn. In other embodiments, the combination of two doping elements isMg/N. In other embodiments, the combination of two doping elements isCa/S. In other embodiments, the combination of two doping elements isRb/S. In other embodiments, the combination of two doping elements isSr/Nd. In other embodiments, the combination of two doping elements isEu/Y. In other embodiments, the combination of two doping elements isMg/Nd. In other embodiments, the combination of two doping elements isSr/Na. In other embodiments, the combination of two doping elements isNd/Mg. In other embodiments, the combination of two doping elements isLa/Mg. In other embodiments, the combination of two doping elements isYb/S. In other embodiments, the combination of two doping elements isMg/Na. In other embodiments, the combination of two doping elements isSr/W. In other embodiments, the combination of two doping elements isK/La. In other embodiments, the combination of two doping elements isK/Na. In other embodiments, the combination of two doping elements isLi/Cs. In other embodiments, the combination of two doping elements isLi/Na. In other embodiments, the combination of two doping elements isZn/K. In other embodiments, the combination of two doping elements isLi/K. In other embodiments, the combination of two doping elements isRb/Hf. In other embodiments, the combination of two doping elements isCa/Cs. In other embodiments, the combination of two doping elements isHf/Bi. In other embodiments, the combination of two doping elements isSr/Sn. In other embodiments, the combination of two doping elements isSr/W. In other embodiments, the combination of two doping elements isSr/Nb. In other embodiments, the combination of two doping elements isZr/W. In other embodiments, the combination of two doping elements isY/W. In other embodiments, the combination of two doping elements isNa/W. In other embodiments, the combination of two doping elements isBi/W. In other embodiments, the combination of two doping elements isBi/Cs. In other embodiments, the combination of two doping elements isBi/Ca. In other embodiments, the combination of two doping elements isBi/Sn. In other embodiments, the combination of two doping elements isBi/Sb. In other embodiments, the combination of two doping elements isGe/Hf. In other embodiments, the combination of two doping elements isHf/Sm. In other embodiments, the combination of two doping elements isSb/Ag. In other embodiments, the combination of two doping elements isSb/Bi. In other embodiments, the combination of two doping elements isSb/Au. In other embodiments, the combination of two doping elements isSb/Sm. In other embodiments, the combination of two doping elements isSb/Sr. In other embodiments, the combination of two doping elements isSb/W. In other embodiments, the combination of two doping elements isSb/Hf. In other embodiments, the combination of two doping elements isSb/Yb. In other embodiments, the combination of two doping elements isSb/Sn. In other embodiments, the combination of two doping elements isYb/Au. In other embodiments, the combination of two doping elements isYb/Ta. In other embodiments, the combination of two doping elements isYb/W. In other embodiments, the combination of two doping elements isYb/Sr. In other embodiments, the combination of two doping elements isYb/Pb. In other embodiments, the combination of two doping elements isYb/W. In other embodiments, the combination of two doping elements isYb/Ag. In other embodiments, the combination of two doping elements isAu/Sr. In other embodiments, the combination of two doping elements isW/Ge. In other embodiments, the combination of two doping elements isTa/Hf. In other embodiments, the combination of two doping elements isW/Au. In other embodiments, the combination of two doping elements isCa/W. In other embodiments, the combination of two doping elements isAu/Re. In other embodiments, the combination of two doping elements isSm/Li. In other embodiments, the combination of two doping elements isLa/K. In other embodiments, the combination of two doping elements isZn/Cs. In other embodiments, the combination of two doping elements isZr/Cs. In other embodiments, the combination of two doping elements isCa/Ce. In other embodiments, the combination of two doping elements isLi/Sr. In other embodiments, the combination of two doping elements isCs/Zn. In other embodiments, the combination of two doping elements isDy/K. In other embodiments, the combination of two doping elements isLa/Mg. In other embodiments, the combination of two doping elements isIn/Sr. In other embodiments, the combination of two doping elements isSr/Cs. In other embodiments, the combination of two doping elements isGa/Cs. In other embodiments, the combination of two doping elements isLu/Fe. In other embodiments, the combination of two doping elements isSr/Tm. In other embodiments, the combination of two doping elements isLa/Dy. In other embodiments, the combination of two doping elements isMg/K. In other embodiments, the combination of two doping elements isZr/K. In other embodiments, the combination of two doping elements isLi/Cs. In other embodiments, the combination of two doping elements isSm/Cs. In other embodiments, the combination of two doping elements isIn/K. In other embodiments, the combination of two doping elements isLu/Tl. In other embodiments, the combination of two doping elements isPr/Zn. In other embodiments, the combination of two doping elements isLu/Nb. In other embodiments, the combination of two doping elements isNa/Pt. In other embodiments, the combination of two doping elements isNa/Ce. In other embodiments, the combination of two doping elements isBa/Ta. In other embodiments, the combination of two doping elements isCu/Sn. In other embodiments, the combination of two doping elements isAg/Au. In other embodiments, the combination of two doping elements isAl/Bi. In other embodiments, the combination of two doping elements isAl/Mo. In other embodiments, the combination of two doping elements isAl/Nb. In other embodiments, the combination of two doping elements isAu/Pt. In other embodiments, the combination of two doping elements isGa/Bi. In other embodiments, the combination of two doping elements isMg/W. In other embodiments, the combination of two doping elements isPb/Au. In other embodiments, the combination of two doping elements isSn/Mg. In other embodiments, the combination of two doping elements isZn/Bi. In other embodiments, the combination of two doping elements isGd/Ho. In other embodiments, the combination of two doping elements isZr/Bi. In other embodiments, the combination of two doping elements isHo/Sr. In other embodiments, the combination of two doping elements isCa/Sr. In other embodiments, the combination of two doping elements isSr/Pb. In other embodiments, the combination of two doping elements isSr/Hf.

In still other embodiments, the nanowire catalysts comprise a rare earthoxide and dopants selected from at least one of the followingcombinations Mg/La/K, Na/Dy/K, Na/La/Dy, Na/La/Eu, Na/La/K, K/La/S,Li/Cs/La, Li/Sr/Cs, Li/Ga/Cs, Li/Na/Sr, Li/Sm/Cs, Cs/K/La, Sr/Cs/La,Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca, Rb/Sr/Lu, Na/Eu/Hf, Dy/Rb/Gd, Na/Pt/Bi,Ca/Mg/Na, Na/K/Mg, Na/Li/Cs, La/Dy/K, Sm/Li/Sr, Li/Rb/Ga, Li/Cs/Tm,Li/K/La, Ce/Zr/La, Ca/Al/La, Sr/Zn/La, Cs/La/Na, La/S/Sr, Rb/Sr/La,Na/Sr/Lu, Sr/Eu/Dy, La/Dy/Gd, Gd/Li/K, Rb/K/Lu, Na/Ce/Co, Ba/Rh/Ta,Na/Al/Bi, Cs/Eu/S, Sm/Tm/Yb, Hf/Zr/Ta, Na/Ca/Lu, Gd/Ho/Sr, Ca/Sr/W,Na/Zr/Eu/Tm, Sr/W/Li, Ca/Sr/W or Mg/Nd/Fe.

In more embodiments, the nanowire catalysts comprise a rare earth oxideand dopants selected from at least one of the following combinationsNd/Sr/CaO, La/Nd/Sr, La/Bi/Sr, Mg/Nd/Fe, Mg/La/K, Na/Dy/K, Na/La/Dy,Na/La/Eu, Na/La/K, K/La/S, Li/Cs/La, Li/Sr/Cs, Li/Ga/Cs, Li/Na/Sr,Li/Sm/Cs, Cs/K/La, Sr/Cs/La, Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca, Rb/Sr/Lu,Na/Eu/Hf, Dy/Rb/Gd, Na/Pt/Bi, Ca/Mg/Na, Na/K/Mg, Na/Li/Cs, La/Dy/K,Sm/Li/Sr, Li/Rb/Ga, Li/Cs/Tm, Li/K/La, Ce/Zr/La, Ca/Al/La, Sr/Zn/La,Cs/La/Na, La/S/Sr, Rb/Sr/La, Na/Sr/Lu, Sr/Eu/Dy, La/Dy/Gd, Gd/Li/K,Rb/K/Lu, Na/Ce/Co, Ba/Rh/Ta, Na/Al/Bi, Cs/Eu/S, Sm/Tm/Yb, Hf/Zr/Ta,Na/Ca/Lu, Gd/Ho/Sr, Ca/Sr/W, Na/Zr/Eu/Tm, Sr/W/Li or Ca/Sr/W.

In other embodiments of the foregoing rare earth oxide nanowirecatalysts, the nanowire catalysts comprise a combination of at leastthree doping elements. In some embodiments, the combination of at leastthree different doping elements is Nd/Sr/CaO. In other embodiments, thecombination of at least three different doping elements is La/Nd/Sr. Inother embodiments, the combination of at least three different dopingelements is La/Bi/Sr. In other embodiments, the combination of at leastthree different doping elements is Mg/Nd/Fe. In other embodiments, thecombination of at least three different doping elements is Mg/La/K. Inother embodiments, the combination of at least three different dopingelements is Na/Dy/K. In other embodiments, the combination of at leastthree different doping elements is Na/La/Dy. In other embodiments, thecombination of at least three different doping elements is Na/La/Eu. Inother embodiments, the combination of at least three different dopingelements is Na/La/K. In other embodiments, the combination of at leastthree different doping elements is K/La/S. In other embodiments, thecombination of at least three different doping elements is Li/Cs/La. Inother embodiments, the combination of at least three different dopingelements is Li/Sr/Cs. In other embodiments, the combination of at leastthree different doping elements is Li/Ga/Cs. In other embodiments, thecombination of at least three different doping elements is Li/Na/Sr. Inother embodiments, the combination of at least three different dopingelements is Li/Sm/Cs. In other embodiments, the combination of at leastthree different doping elements is Cs/K/La. In other embodiments, thecombination of at least three different doping elements is Sr/Cs/La. Inother embodiments, the combination of at least three different dopingelements is Sr/Ho/Tm. In other embodiments, the combination of at leastthree different doping elements is La/Nd/S. In other embodiments, thecombination of at least three different doping elements is Li/Rb/Ca. Inother embodiments, the combination of at least three different dopingelements is Rb/Sr/Lu. In other embodiments, the combination of at leastthree different doping elements is Na/Eu/Hf. In other embodiments, thecombination of at least three different doping elements is Dy/Rb/Gd. Inother embodiments, the combination of at least three different dopingelements is Na/Pt/Bi. In other embodiments, the combination of at leastthree different doping elements is Ca/Mg/Na. In other embodiments, thecombination of at least three different doping elements is Na/K/Mg. Inother embodiments, the combination of at least three different dopingelements is Na/Li/Cs. In other embodiments, the combination of at leastthree different doping elements is La/Dy/K. In other embodiments, thecombination of at least three different doping elements is Sm/Li/Sr. Inother embodiments, the combination of at least three different dopingelements is Li/Rb/Ga. In other embodiments, the combination of at leastthree different doping elements is Li/Cs/Tm. In other embodiments, thecombination of at least three different doping elements is Li/K/La. Inother embodiments, the combination of at least three different dopingelements is Ce/Zr/La. In other embodiments, the combination of at leastthree different doping elements is Ca/Al/La. In other embodiments, thecombination of at least three different doping elements is Sr/Zn/La. Inother embodiments, the combination of at least three different dopingelements is Cs/La/Na. In other embodiments, the combination of at leastthree different doping elements is La/S/Sr. In other embodiments, thecombination of at least three different doping elements is Rb/Sr/La. Inother embodiments, the combination of at least three different dopingelements is Na/Sr/Lu. In other embodiments, the combination of at leastthree different doping elements is Sr/Eu/Dy. In other embodiments, thecombination of at least three different doping elements is La/Dy/Gd. Inother embodiments, the combination of at least three different dopingelements is Gd/Li/K. In other embodiments, the combination of at leastthree different doping elements is Rb/K/Lu. In other embodiments, thecombination of at least three different doping elements is Na/Ce/Co. Inother embodiments, the combination of at least three different dopingelements is Ba/Rh/Ta. In other embodiments, the combination of at leastthree different doping elements is Na/Al/Bi. In other embodiments, thecombination of at least three different doping elements is Cs/Eu/S. Inother embodiments, the combination of at least three different dopingelements is Sm/Tm/Yb. In other embodiments, the combination of at leastthree different doping elements is Hf/Zr/Ta. In other embodiments, thecombination of at least three different doping elements is Na/Ca/Lu. Inother embodiments, the combination of at least three different dopingelements is Gd/Ho/Sr. In other embodiments, the combination of at leastthree different doping elements is Ca/Sr/W. In other embodiments, thecombination of at least three different doping elements is Na/Zr/Eu/Tm.In other embodiments, the combination of at least three different dopingelements is Sr/W/Li. In other embodiments, the combination of at leastthree different doping elements is Ca/Sr/W.

As noted above, certain doping combinations have been found useful invarious catalytic reactions, such as OCM. Thus, in one embodiment, thecatalytic nanowire comprises a combination of at least four differentdoping elements, wherein the doping elements are selected from a metalelement, a semi-metal element and a non-metal element. For example incertain embodiments the catalytic nanowire comprises a metal oxide, andin other embodiments the catalytic nanowire comprises a lanthanidemetal. Still other embodiments provide a catalytic nanowire comprisingLa₂O₃, Nd₂O₃, Yb₂O₃, Eu₂O₃, Sm₂O₃, Y₂O₃, Ce₂O₃, Pr₂O₃ or combinationsthereof. In still other embodiments, the doping elements do not includeat least one of Li, B, Na, Co or Ga, and in other embodiments thenanowires do not comprise Mg and/or Mn.

In other embodiments, the catalytic nanowire comprises a lanthanideoxide, for example a lanthanide mixed oxide, for example in someembodiments the catalytic nanowire comprises Ln1_(4-x)Ln2_(x)O₆, whereinLn1 and Ln2 are each independently a lanthanide element, wherein Ln1 andLn2 are not the same and x is a number ranging from greater than 0 toless than 4. In other embodiments, the catalytic nanowire comprisesLa_(4-x)Nd_(x)O₆, wherein x is a number ranging from greater than 0 toless than 4, and in still other embodiments, the catalytic nanowirecomprises La₃NdO₆, LaNd₃O₆, La_(1.5)Nd_(2.5)O₆, La_(2.5)Nd_(1.5)O₆,La_(3.2)Nd_(0.8)O₆, La_(3.5)Nd_(0.5)O₆, La_(3.8)Nd_(0.2)O₆ orcombinations thereof. In certain other embodiments the mixed oxidecomprises Y—La, Zr—La, Pr—La, Ce—La or combinations thereof.

In other embodiments, the doping elements are selected from Eu, Na, Sr,Ca, Mg, Sm, Ho, Tm, W, La, K, Dy, In, Li, Cs, S, Zn, Ga, Rb, Ba, Yb, Ni,Lu, Ta, P, Hf, Tb, Gd, Pt, Bi, Sn, Nb, Sb, Ge, Ag, Au, Pb, B, Re, Fe,Al, Zr, Tl, Pr, Co, Ce, Rh, and Mo. For example, in some embodiments,the combination of at least four different doping elements is:Na/Zr/Eu/Ca, Sr/Sm/Ho/Tm, Na/K/Mg/Tm, Na/La/Eu/In, Na/La/Li/Cs,Li/Cs/La/Tm, Li/Cs/Sr/Tm, Li/Sr/Cs, Li/Sr/Zn/K, Li/K/Sr/La, Li/Na/Rb/Ga,Li/Na/Sr/La, Ba/Sm/Yb/S, Ba/Tm/K/La, Ba/Tm/Zn/K, Cs/La/Tm/Na,Cs/Li/K/La, Sm/Li/Sr/Cs, Sr/Tm/Li/Cs, Zr/Cs/K/La, Rb/Ca/In/Ni,Tm/Lu/Ta/P, Rb/Ca/Dy/P, Mg/La/Yb/Zn, Na/Sr/Lu/Nb, Na/Nd/In/K,Rb/Ga/Tm/Cs, K/La/Zr/Ag, Ho/Cs/Li/La, K/La/Zr/Ag, Na/Sr/Eu/Ca,K/Cs/Sr/La, Na/Mg/Tl/P, Sr/La/Dy/S, Na/Ga/Gd/Al, Sm/Tm/Yb/Fe,Rb/Gd/Li/K, Gd/Ho/Al/P, Na/Zr/Eu/Tm Sr/Ho/Tm/Na or Rb/Ga/Tm/Cs orLa/Bi/Ce/Nd/Sr.

In other embodiments, the combination of at least four different dopingelements is Sr/Sm/Ho/Tm. In other embodiments, the combination of atleast four different doping elements is Na/K/Mg/Tm. In otherembodiments, the combination of at least four different doping elementsis Na/La/Eu/In. In other embodiments, the combination of at least fourdifferent doping elements is Na/La/Li/Cs. In other embodiments, thecombination of at least four different doping elements is Li/Cs/La/Tm.In other embodiments, the combination of at least four different dopingelements is Li/Cs/Sr/Tm. In other embodiments, the combination of atleast four different doping elements is Li/Sr/Zn/K. In otherembodiments, the combination of at least four different doping elementsis Li/Ga/Cs. In other embodiments, the combination of at least fourdifferent doping elements is Li/K/Sr/La. In other embodiments, thecombination of at least four different doping elements is Li/Na/Rb/Ga.In other embodiments, the combination of at least four different dopingelements is Li/Na/Sr/La. In other embodiments, the combination of atleast four different doping elements is Ba/Sm/Yb/S. In otherembodiments, the combination of at least four different doping elementsis Ba/Tm/K/La. In other embodiments, the combination of at least fourdifferent doping elements is Ba/Tm/Zn/K. In other embodiments, thecombination of at least four different doping elements is Cs/La/Tm/Na.In other embodiments, the combination of at least four different dopingelements is Cs/Li/K/La. In other embodiments, the combination of atleast four different doping elements is Sm/Li/Sr/Cs. In otherembodiments, the combination of at least four different doping elementsis Sr/Tm/Li/Cs. In other embodiments, the combination of at least fourdifferent doping elements is Zr/Cs/K/La. In other embodiments, thecombination of at least four different doping elements is Rb/Ca/In/Ni.In other embodiments, the combination of at least four different dopingelements is Tm/Lu/Ta/P. In other embodiments, the combination of atleast four different doping elements is Rb/Ca/Dy/P. In otherembodiments, the combination of at least four different doping elementsis Mg/La/Yb/Zn. In other embodiments, the combination of at least fourdifferent doping elements is Na/Sr/Lu/Nb. In other embodiments, thecombination of at least four different doping elements is Na/Nd/In/K. Inother embodiments, the combination of at least four different dopingelements is K/La/Zr/Ag. In other embodiments, the combination of atleast four different doping elements is Ho/Cs/Li/La. In otherembodiments, the combination of at least four different doping elementsis K/La/Zr/Ag. In other embodiments, the combination of at least fourdifferent doping elements is Na/Sr/Eu/Ca. In other embodiments, thecombination of at least four different doping elements is K/Cs/Sr/La. Inother embodiments, the combination of at least four different dopingelements is Na/Mg/Tl/P. In other embodiments, the combination of atleast four different doping elements is Sr/La/Dy/S. In otherembodiments, the combination of at least four different doping elementsis Na/Ga/Gd/Al. In other embodiments, the combination of at least fourdifferent doping elements is Sm/Tm/Yb/Fe. In other embodiments, thecombination of at least four different doping elements is Rb/Gd/Li/K. Inother embodiments, the combination of at least four different dopingelements is Gd/Ho/Al/P. In other embodiments, the combination of atleast four different doping elements is Na/Zr/Eu/T. In otherembodiments, the combination of at least four different doping elementsis Sr/Ho/Tm/Na. In other embodiments, the combination of at least fourdifferent doping elements is Na/Zr/Eu/Ca. In other embodiments, thecombination of at least four different doping elements is Rb/Ga/Tm/Cs.In other embodiments, the combination of at least four different dopingelements is La/Bi/Ce/Nd/Sr.

In other embodiments, the catalytic nanowire comprises at least twodifferent doping elements, wherein the doping elements are selected froma metal element, a semi-metal element and a non-metal element, andwherein at least one of the doping elements is K, Sc, Ti, V, Nb, Ru, Os,Ir, Cd, In, Tl, S, Se, Po, Pr, Tb, Dy, Ho, Er, Tm, Lu or an elementselected from any of groups 6, 7, 10, 11, 14, 15 or 17. In someembodiments, at least one of the doping elements is K, Ti, V, Nb, Ru,Os, Ir, Cd, In, Tl, S, Se, Po, Pr, Tb, Dy, Ho, Er, Tm, Lu or an elementselected from any of groups 10, 11, 14, 15 or 17. In certain otherembodiments of the foregoing catalytic nanowire, the catalytic nanowirecomprises a metal oxide, and in other embodiments the catalytic nanowirecomprises a lanthanide metal. In still other embodiments the catalyticnanowire comprises La₂O₃, Nd₂O₃, Yb₂O₃, Eu₂O₃, Sm₂O₃, Y₂O₃, Ce₂O₃, Pr₂O₃or combinations thereof.

In other embodiments of the foregoing catalytic nanowire, the catalyticnanowire comprises a lanthanide oxide, for example a lanthanide mixedoxide, for example in some embodiments the catalytic nanowire comprisesLn1_(4-x)Ln2_(x)O₆, wherein Ln1 and Ln2 are each independently alanthanide element, wherein Ln1 and Ln2 are not the same and x is anumber ranging from greater than 0 to less than 4. In other embodiments,the catalytic nanowire comprises La_(4-x)Nd_(x)O₆, wherein x is a numberranging from greater than 0 to less than 4, and in still otherembodiments, the catalytic nanowire comprises La₃NdO₆, LaNd₃O₆,La_(1.5)Nd_(2.5)O₆, La_(2.5)Nd_(1.5)O₆, La_(3.2)Nd_(0.8)O₆,La_(3.5)Nd_(0.5)O₆, La_(3.8)Nd_(0.2)O₆ or combinations thereof. Incertain other embodiments the mixed oxide comprises Y—La, Zr—La, Pr—La,Ce—La or combinations thereof.

In other embodiments of the nanowire comprising at least two dopingelements, the doping elements are selected from Eu, Na, Sr, Ca, Mg, Sm,Ho, Tm, W, La, K, Dy, In, Li, Cs, S, Zn, Ga, Rb, Ba, Yb, Ni, Lu, Ta, P,Hf, Tb, Gd, Pt, Bi, Sn, Nb, Sb, Ge, Ag, Au, Pb, B, Re, Fe, Al, Zr, Tl,Pr, Co, Ce, Rh, and Mo.

In yet another aspect, the present disclosure provides a catalyticnanowire comprising at least one of the following dopant combinations:Eu/Na, Sr/Na, Na/Zr/Eu/Ca, Mg/Na, Sr/Sm/Ho/Tm, Sr/W, Mg/La/K,Na/K/Mg/Tm, Na/Dy/K, Na/La/Dy, Sr/Hf/K, Na/La/Eu, Na/La/Eu/In, Na/La/K,Na/La/Li/Cs, K/La, K/La/S, K/Na, Li/Cs, Li/Cs/La, Li/Cs/La/Tm,Li/Cs/Sr/Tm, Li/Sr/Cs, Li/Sr/Zn/K, Li/Ga/Cs, Li/K/Sr/La, Li/Na,Li/Na/Rb/Ga, Li/Na/Sr, Li/Na/Sr/La, Sr/Zr, Li/Sm/Cs, Ba/Sm/Yb/S,Ba/Tm/K/La, Ba/Tm/Zn/K, Sr/Zr/K, Cs/K/La, Cs/La/Tm/Na, Cs/Li/K/La,Sm/Li/Sr/Cs, Sr/Cs/La, Sr/Tm/Li/Cs, Zn/K, Zr/Cs/K/La, Rb/Ca/In/Ni,Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca, Li/K, Tm/Lu/Ta/P, Rb/Ca/Dy/P, Mg/La/Yb/Zn,Rb/Sr/Lu, Na/Sr/Lu/Nb, Na/Eu/Hf, Dy/Rb/Gd, Sr/Ce, Na/Pt/Bi, Rb/Hf,Ca/Cs, Ca/Mg/Na, Hf/Bi, Sr/Sn, Sr/W, Sr/Nb, Sr/Ce/K, Zr/W, Y/W, Na/W,Bi/W, Bi/Cs, Bi/Ca, Bi/Sn, Bi/Sb, Ge/Hf, Hf/Sm, Sb/Ag, Sb/Bi, Sb/Au,Sb/Sm, Sb/Sr, Sb/W, Sb/Hf, Sb/Yb, Sb/Sn, Yb/Au, Yb/Ta, Yb/W, Yb/Sr,Yb/Pb, Yb/W, Yb/Ag, Au/Sr, W/Ge, Sr/Tb, Ta/Hf, W/Au, Ca/W, Au/Re, Sm/Li,La/K, Zn/Cs, Na/K/Mg, Zr/Cs, Ca/Ce, Na/Li/Cs, Li/Sr, Cs/Zn, La/Dy/K,Dy/K, La/Mg, Na/Nd/In/K, In/Sr, Sr/Cs, Rb/Ga/Tm/Cs, Ga/Cs, K/La/Zr/Ag,Lu/Fe, Sr/Tb/K, Sr/Tm, La/Dy, Sm/Li/Sr, Mg/K, Sr/Pr, Li/Rb/Ga, Li/Cs/Tm,Zr/K, Li/Cs, Li/K/La, Ce/Zr/La, Ca/Al/La, Sr/Zn/La, Sr/Cs/Zn, Sm/Cs,In/K, Ho/Cs/Li/La, Sr/Pr/K, Cs/La/Na, La/S/Sr, K/La/Zr/Ag, Lu/Tl, Pr/Zn,Rb/Sr/La, Na/Sr/Eu/Ca, K/Cs/Sr/La, Na/Sr/Lu, Sr/Eu/Dy, Lu/Nb, La/Dy/Gd,Na/Mg/Tl/P, Na/Pt, Gd/Li/K, Rb/K/Lu, Sr/La/Dy/S, Na/Ce/Co, Na/Ce,Na/Ga/Gd/Al, Ba/Rh/Ta, Ba/Ta, Na/Al/Bi, Sr/Hf/Rb, Cs/Eu/S, Sm/Tm/Yb/Fe,Sm/Tm/Yb, Hf/Zr/Ta, Rb/Gd/Li/K, Gd/Ho/Al/P, Na/Ca/Lu, Cu/Sn, Ag/Au,Al/Bi, Al/Mo, Al/Nb, Au/Pt, Ga/Bi, Mg/W, Pb/Au, Sn/Mg, Sr/B, Zn/Bi,Gd/Ho, Zr/Bi, Ho/Sr, Gd/Ho/Sr, Ca/Sr, Ca/Sr/W, Sr/Ho/Tm/Na, Na/Zr/Eu/Tm,Sr/Ho/Tm/Na, Sr/Pb, Sr/W/Li, Ca/Sr/W or Sr/Hf.

In other embodiments of the foregoing catalytic nanowire, the dopant isselected from Cs/Eu/S, Sm/Tm/Yb/Fe, Sm/Tm/Yb, Hf/Zr/Ta, Rb/Gd/Li/K,Gd/Ho/Al/P, Na/Ca/Lu, Cu/Sn, Ag/Au, Al/Bi, Al/Mo, Al/Nb, Au/Pt, Ga/Bi,Mg/W, Pb/Au, Sn/Mg, Zn/Bi, Gd/Ho, Zr/Bi, Ho/Sr, Gd/Ho/Sr, Ca/Sr,Ca/Sr/W, Na/Zr/Eu/Tm, Sr/Ho/Tm/Na, Sr/Pb, Ca, Sr/W/Li, Ca/Sr/W, Sr/Hf,Eu/Na, Sr/Na, Na/Zr/Eu/Ca, Mg/Na, Sr/Sm/Ho/Tm, Sr/W, Mg/La/K,Na/K/Mg/Tm, Na/Dy/K, Na/La/Dy, Na/La/Eu, Na/La/Eu/In, Na/La/K,Na/La/Li/Cs, K/La, K/La/S, K/Na, Li/Cs, Li/Cs/La, Li/Cs/La/Tm,Li/Cs/Sr/Tm, Li/Sr/Cs, Li/Sr/Zn/K, Li/Ga/Cs, Li/K/Sr/La, Li/Na,Li/Na/Rb/Ga and Li/Na/Sr.

In still other embodiments of the foregoing catalytic nanowire thedopant is selected from Li/Na/Sr/La, Li/Sm/Cs, Ba/Sm/Yb/S, Ba/Tm/K/La,Ba/Tm/Zn/K, Cs/K/La, Cs/La/Tm/Na, Cs/Li/K/La, Sm/Li/Sr/Cs, Sr/Cs/La,Sr/Tm/Li/Cs, Zn/K, Zr/Cs/K/La, Rb/Ca/In/Ni, Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca,Li/K, Tm/Lu/Ta/P, Rb/Ca/Dy/P, Mg/La/Yb/Zn, Rb/Sr/Lu, Na/Sr/Lu/Nb,Na/Eu/Hf, Dy/Rb/Gd, Na/Pt/Bi, Rb/Hf, Ga/Cs, K/La/Zr/Ag, Lu/Fe, Sr/Tm,La/Dy, Sm/Li/Sr, Mg/K, Li/Rb/Ga, Li/Cs/Tm, Zr/K, Li/Cs, Li/K/La,Ce/Zr/La, Ca/Al/La, Sr/Zn/La, Sr/Cs/Zn, Sm/Cs, In/K, Ho/Cs/Li/La,Cs/La/Na, La/S/Sr, K/La/Zr/Ag, Lu/Tl, Pr/Zn, Rb/Sr/La, Na/Sr/Eu/Ca,K/Cs/Sr/La, Na/Sr/Lu, Sr/Eu/Dy, Lu/Nb, La/Dy/Gd, Na/Mg/Tl/P, Na/Pt,Gd/Li/K, Rb/K/Lu, Sr/La/Dy/S, Na/Ce/Co, Na/Ce, Na/Ga/Gd/Al, Ba/Rh/Ta,Ba/Ta, Na/Al/Bi, Cs/Eu/S, Sm/Tm/Yb/Fe, Sm/Tm/Yb, Hf/Zr/Ta, Rb/Gd/Li/K,Gd/Ho/Al/P and Na/Ca/Lu.

In still other embodiments of the foregoing catalytic nanowire, thedopant is selected from Ta/Hf, W/Au, Ca/W, Au/Re, Sm/Li, La/K, Zn/Cs,Na/K/Mg, Zr/Cs, Ca/Ce, Na/Li/Cs, Li/Sr, Cs/Zn, La/Dy/K, Dy/K, La/Mg,Na/Nd/In/K, In/Sr, Sr/Cs, Rb/Ga/Tm/Cs, Ga/Cs, K/La/Zr/Ag, Lu/Fe, Sr/Tm,La/Dy, Sm/Li/Sr, Mg/K, Li/Rb/Ga, Li/Cs/Tm, Zr/K, Li/Cs, Li/K/La,Ce/Zr/La, Ca/Al/La, Sr/Zn/La, Sr/Cs/Zn, Sm/Cs, In/K, Ho/Cs/Li/La,Cs/La/Na, La/S/Sr, K/La/Zr/Ag, Lu/Tl, Pr/Zn, Rb/Sr/La, Na/Sr/Eu/Ca,K/Cs/Sr/La, Na/Sr/Lu, Sr/Eu/Dy, Lu/Nb, La/Dy/Gd, Na/Mg/Tl/P, Na/Pt,Gd/Li/K, Li/Sr/Cs, Li/Sr/Zn/K, Li/Ga/Cs, Li/K/Sr/La, Li/Na, Li/Na/Rb/Ga,Li/Na/Sr, Li/Na/Sr/La, Li/Sm/Cs, Ba/Sm/Yb/S, Ba/Tm/K/La, Ba/Tm/Zn/K,Cs/K/La, Cs/La/Tm/Na, Cs/Li/K/La, Sm/Li/Sr/Cs, Sr/Cs/La, Sr/Tm/Li/Cs,Zn/K, Zr/Cs/K/La, Rb/Ca/In/Ni, Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca, Li/K,Tm/Lu/Ta/P, Rb/Ca/Dy/P, Mg/La/Yb/Zn, Rb/Sr/Lu, Na/Sr/Lu/Nb, Na/Eu/Hf,Dy/Rb/Gd, Na/Pt/Bi, Rb/Hf, Ca/Cs, Ca/Mg/Na, Hf/Bi, Sr/Sn, Sr/W, Sr/Nb,Zr/W, Y/W, Na/W, Bi/W, Bi/Cs, Bi/Ca, Bi/Sn, Bi/Sb, Ge/Hf, Hf/Sm, Sb/Ag,Sb/Bi, Sb/Au, Sb/Sm, Sb/Sr, Sb/W, Sb/Hf, Sb/Yb, Sb/Sn, Yb/Au, Yb/Ta,Yb/W, Yb/Sr, Yb/Pb, Yb/W, Yb/Ag, Au/Sr and W/Ge.

For example in certain embodiments of the foregoing catalytic nanowire,the catalytic nanowire comprises a metal oxide, and in other embodimentsthe catalytic nanowire comprises a lanthanide metal. In still otherembodiments, the catalytic nanowire comprises La₂O₃, Nd₂O₃, Yb₂O₃,Eu₂O₃, Sm₂O₃, Y₂O₃, Ce₂O₃, Pr₂O₃ or combinations thereof.

In other embodiments of the foregoing nanowire, the catalytic nanowirecomprises a lanthanide oxide, for example a lanthanide mixed oxide, forexample in some embodiments the catalytic nanowire comprisesLn1_(4-x)Ln2_(x)O₆, wherein Ln1 and Ln2 are each independently alanthanide element, wherein Ln1 and Ln2 are not the same and x is anumber ranging from greater than 0 to less than 4. In other embodiments,the catalytic nanowire comprises La_(4-x)Nd_(x)O₆, wherein x is a numberranging from greater than 0 to less than 4, and in still otherembodiments, the catalytic nanowire comprises La₃NdO₆, LaNd₃O₆,La_(1.5)Nd_(2.5)O₆, La_(2.5)Nd_(1.5)O₆, La_(3.2)Nd_(0.8)O₆,La_(3.5)Nd_(0.5)O₆, La_(3.8)Nd_(0.2)O₆ or combinations thereof. Incertain other embodiments the mixed oxide comprises Y—La, Zr—La, Pr—La,Ce—La or combinations thereof.

In still other embodiments, the disclosure provides a catalytic nanowirecomprising Ln1_(4-x)Ln2_(x)O₆ and a dopant comprising a metal element, asemi-metal element, a non-metal element or combinations thereof, whereinLn1 and Ln2 are each independently a lanthanide element, wherein Ln1 andLn2 are not the same and x is a number ranging from greater than 0 toless than 4. For example, in certain embodiments the catalytic nanowirecomprises La_(4-x)Ln1_(x)O₆, wherein Ln1 is a lanthanide element and xis a number ranging from greater than 0 to less than 4, and in otherspecific embodiments, the catalytic nanowire comprises La_(4-x)Nd_(x)O₆,wherein x is a number ranging from greater than 0 to less than 4.

Still further embodiments of the foregoing nanowire include embodimentswherein the catalytic nanowire comprises comprises La₃NdO₆, LaNd₃O₆,La_(1.5)Nd_(2.5)O₆, La_(2.5)Nd_(1.5)O₆, La_(3.2)Nd_(0.8)O₆,La₃₅Nd_(0.5)O₆, La₃₈Nd_(0.2)O₆ or combinations thereof.

In other embodiments, the dopant is selected from: Eu, Na, Sr, Ca, Mg,Sm, Ho, Tm, W, La, K, Dy, In, Li, Cs, S, Zn, Ga, Rb, Ba, Yb, Ni, Lu, Ta,P, Hf, Tb, Gd, Pt, Bi, Sn, Nb, Sb, Ge, Ag, Au, Pb, B, Re, Fe, Al, Zr,Tl, Pr, Co, Ce, Rh, and Mo. For example in certain embodiments, thecatalytic nanowire comprises at least one of the following dopantcombinations: Eu/Na, Sr/Na, Na/Zr/Eu/Ca, Mg/Na, Sr/Sm/Ho/Tm, Sr/W,Mg/La/K, Na/K/Mg/Tm, Na/Dy/K, Na/La/Dy, Sr/Hf/K, Na/La/Eu, Na/La/Eu/In,Na/La/K, Na/La/Li/Cs, K/La, K/La/S, K/Na, Li/Cs, Li/Cs/La, Li/Cs/La/Tm,Li/Cs/Sr/Tm, Li/Sr/Cs, Li/Sr/Zn/K, Li/Ga/Cs, Li/K/Sr/La, Li/Na,Li/Na/Rb/Ga, Li/Na/Sr, Li/Na/Sr/La, Sr/Zr, Li/Sm/Cs, Ba/Sm/Yb/S,Ba/Tm/K/La, Ba/Tm/Zn/K, Sr/Zr/K, Cs/K/La, Cs/La/Tm/Na, Cs/Li/K/La,Sm/Li/Sr/Cs, Sr/Cs/La, Sr/Tm/Li/Cs, Zn/K, Zr/Cs/K/La, Rb/Ca/In/Ni,Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca, Li/K, Tm/Lu/Ta/P, Rb/Ca/Dy/P, Mg/La/Yb/Zn,Rb/Sr/Lu, Na/Sr/Lu/Nb, Na/Eu/Hf, Dy/Rb/Gd, Sr/Ce, Na/Pt/Bi, Rb/Hf,Ca/Cs, Ca/Mg/Na, Hf/Bi, Sr/Sn, Sr/W, Sr/Nb, Sr/Ce/K, Zr/W, Y/W, Na/W,Bi/W, Bi/Cs, Bi/Ca, Bi/Sn, Bi/Sb, Ge/Hf, Hf/Sm, Sb/Ag, Sb/Bi, Sb/Au,Sb/Sm, Sb/Sr, Sb/W, Sb/Hf, Sb/Yb, Sb/Sn, Yb/Au, Yb/Ta, Yb/W, Yb/Sr,Yb/Pb, Yb/W, Yb/Ag, Au/Sr, W/Ge, Sr/Tb, Ta/Hf, W/Au, Ca/W, Au/Re, Sm/Li,La/K, Zn/Cs, Na/K/Mg, Zr/Cs, Ca/Ce, Na/Li/Cs, Li/Sr, Cs/Zn, La/Dy/K,Dy/K, La/Mg, Na/Nd/In/K, In/Sr, Sr/Cs, Rb/Ga/Tm/Cs, Ga/Cs, K/La/Zr/Ag,Lu/Fe, Sr/Tb/K, Sr/Tm, La/Dy, Sm/Li/Sr, Mg/K, Sr/Pr, Li/Rb/Ga, Li/Cs/Tm,Zr/K, Li/Cs, Li/K/La, Ce/Zr/La, Ca/Al/La, Sr/Zn/La, Sr/Cs/Zn, Sm/Cs,In/K, Ho/Cs/Li/La, Sr/Pr/K, Cs/La/Na, La/S/Sr, K/La/Zr/Ag, Lu/Tl, Pr/Zn,Rb/Sr/La, Na/Sr/Eu/Ca, K/Cs/Sr/La, Na/Sr/Lu, Sr/Eu/Dy, Lu/Nb, La/Dy/Gd,Na/Mg/Tl/P, Na/Pt, Gd/Li/K, Rb/K/Lu, Sr/La/Dy/S, Na/Ce/Co, Na/Ce,Na/Ga/Gd/Al, Ba/Rh/Ta, Ba/Ta, Na/Al/Bi, Sr/Hf/Rb, Cs/Eu/S, Sm/Tm/Yb/Fe,Sm/Tm/Yb, Hf/Zr/Ta, Rb/Gd/Li/K, Gd/Ho/Al/P, Na/Ca/Lu, Cu/Sn, Ag/Au,Al/Bi, Al/Mo, Al/Nb, Au/Pt, Ga/Bi, Mg/W, Pb/Au, Sn/Mg, Sr/B, Zn/Bi,Gd/Ho, Zr/Bi, Ho/Sr, Gd/Ho/Sr, Ca/Sr, Ca/Sr/W, Sr/Ho/Tm/Na, Na/Zr/Eu/Tm,Sr/Ho/Tm/Na, Sr/Pb, Sr/W/Li, Ca/Sr/W or Sr/Hf.

In other embodiments, the disclosure provides a nanowire comprising amixed oxide of Y—La, Zr—La, Pr—La, Ce—La or combinations thereof and atleast one dopant selected from a metal element, a semi-metal element anda non-metal element. For example, in some embodiments the at least onedopant is selected from Eu, Na, Sr, Ca, Mg, Sm, Ho, Tm, W, La, K, Dy,In, Li, Cs, S, Zn, Ga, Rb, Ba, Yb, Ni, Lu, Ta, P, Hf, Tb, Gd, Pt, Bi,Sn, Nb, Sb, Ge, Ag, Au, Pb, B, Re, Fe, Al, Zr, Tl, Pr, Co, Ce, Rh, andMo, and in even other embodiments, the catalytic nanowire comprises atleast one of the following dopant combinations: Eu/Na, Sr/Na,Na/Zr/Eu/Ca, Mg/Na, Sr/Sm/Ho/Tm, Sr/W, Mg/La/K, Na/K/Mg/Tm, Na/Dy/K,Na/La/Dy, Sr/Hf/K, Na/La/Eu, Na/La/Eu/In, Na/La/K, Na/La/Li/Cs, K/La,K/La/S, K/Na, Li/Cs, Li/Cs/La, Li/Cs/La/Tm, Li/Cs/Sr/Tm, Li/Sr/Cs,Li/Sr/Zn/K, Li/Ga/Cs, Li/K/Sr/La, Li/Na, Li/Na/Rb/Ga, Li/Na/Sr,Li/Na/Sr/La, Sr/Zr, Li/Sm/Cs, Ba/Sm/Yb/S, Ba/Tm/K/La, Ba/Tm/Zn/K,Sr/Zr/K, Cs/K/La, Cs/La/Tm/Na, Cs/Li/K/La, Sm/Li/Sr/Cs, Sr/Cs/La,Sr/Tm/Li/Cs, Zn/K, Zr/Cs/K/La, Rb/Ca/In/Ni, Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca,Li/K, Tm/Lu/Ta/P, Rb/Ca/Dy/P, Mg/La/Yb/Zn, Rb/Sr/Lu, Na/Sr/Lu/Nb,Na/Eu/Hf, Dy/Rb/Gd, Sr/Ce, Na/Pt/Bi, Rb/Hf, Ca/Cs, Ca/Mg/Na, Hf/Bi,Sr/Sn, Sr/W, Sr/Nb, Sr/Ce/K, Zr/W, Y/W, Na/W, Bi/W, Bi/Cs, Bi/Ca, Bi/Sn,Bi/Sb, Ge/Hf, Hf/Sm, Sb/Ag, Sb/Bi, Sb/Au, Sb/Sm, Sb/Sr, Sb/W, Sb/Hf,Sb/Yb, Sb/Sn, Yb/Au, Yb/Ta, Yb/W, Yb/Sr, Yb/Pb, Yb/W, Yb/Ag, Au/Sr,W/Ge, Sr/Tb, Ta/Hf, W/Au, Ca/W, Au/Re, Sm/Li, La/K, Zn/Cs, Na/K/Mg,Zr/Cs, Ca/Ce, Na/Li/Cs, Li/Sr, Cs/Zn, La/Dy/K, Dy/K, La/Mg, Na/Nd/In/K,In/Sr, Sr/Cs, Rb/Ga/Tm/Cs, Ga/Cs, K/La/Zr/Ag, Lu/Fe, Sr/Tb/K, Sr/Tm,La/Dy, Sm/Li/Sr, Mg/K, Sr/Pr, Li/Rb/Ga, Li/Cs/Tm, Zr/K, Li/Cs, Li/K/La,Ce/Zr/La, Ca/Al/La, Sr/Zn/La, Sr/Cs/Zn, Sm/Cs, In/K, Ho/Cs/Li/La,Sr/Pr/K, Cs/La/Na, La/S/Sr, K/La/Zr/Ag, Lu/Tl, Pr/Zn, Rb/Sr/La,Na/Sr/Eu/Ca, K/Cs/Sr/La, Na/Sr/Lu, Sr/Eu/Dy, Lu/Nb, La/Dy/Gd,Na/Mg/Tl/P, Na/Pt, Gd/Li/K, Rb/K/Lu, Sr/La/Dy/S, Na/Ce/Co, Na/Ce,Na/Ga/Gd/Al, Ba/Rh/Ta, Ba/Ta, Na/Al/Bi, Sr/Hf/Rb, Cs/Eu/S, Sm/Tm/Yb/Fe,Sm/Tm/Yb, Hf/Zr/Ta, Rb/Gd/Li/K, Gd/Ho/Al/P, Na/Ca/Lu, Cu/Sn, Ag/Au,Al/Bi, Al/Mo, Al/Nb, Au/Pt, Ga/Bi, Mg/W, Pb/Au, Sn/Mg, Sr/B, Zn/Bi,Gd/Ho, Zr/Bi, Ho/Sr, Gd/Ho/Sr, Ca/Sr, Ca/Sr/W, Sr/Ho/Tm/Na, Na/Zr/Eu/Tm,Sr/Ho/Tm/Na, Sr/Pb, Sr/W/Li, Ca/Sr/W or Sr/Hf.

In still other embodiments, the invention provides a catalytic nanowirecomprising a mixed oxide of a rare earth element and a Group 13 element,wherein the catalytic nanowire further comprises one or more Group 2elements. In some embodiments, the Group 13 element is B, Al, Ga or In.In other embodiments, the Group 2 element is Ca or Sr. In still otherembodiments, the rare earth element is La, Y, Nd, Yb, Sm, Pr, Ce or Eu.

Examples of the foregoing catalytic nanowires include catalyticnanowires comprising CaLnBO_(x), CaLnAlO_(x), CaLnGaO_(x), CaLnInO_(x),CaLnAlSrO_(x) and CaLnAlSrO_(x), wherein Ln is a lanthanide or yttriumand x is number such that all charges are balanced. For example, in someembodiments, the catalytic nanowire comprises CaLaBO₄, CaLaAlO₄,CaLaGaO₄, CaLaInO₄, CaLaAlSrO₅, CaLaAlSrO₅, CaNdBO₄, CaNdAlO₄, CaNdGaO₄,CaNdInO₄, CaNdAlSrO₄, CaNdAlSrO₄, CaYbBO₄, CaYbAlO₄, CaYbGaO₄, CaYbInO₄,CaYbAlSrO₅, CaYbAlSrO₅, CaEuBO₄, CaEuAlO₄, CaEuGaO₄, CaEuInO₄,CaEuAlSrO₅, CaEuAlSrO₅, CaSmBO₄, CaSmAlO₄, CaSmGaO₄, CaSmInO₄,CaSmAlSrO₅, CaSmAlSrO₅, CaYBO₄, CaYAlO₄, CaYGaO₄, CaYInO₄, CaYAlSrO₅,CaYAlSrO₅, CaCeBO₄, CaCeAlO₄, CaCeGaO₄, CaCeInO₄, CaCeAlSrO₅,CaCeAlSrO₅, CaPrBO₄, CaPrAlO₄, CaPrGaO₄, CaPrInO₄, CaPrAlSrO₅ orCaPrAlSrO₅.

In still other embodiments, the invention is directed to a catalyticnanowire comprising a rare earth oxide, wherein the nanowires are dopedwith a dopant (or dopants) selected from Eu/Na, Sr/Na, Na/Zr/Eu/Ca,Mg/Na, Sr/Sm/Ho/Tm, Sr/W, Mg/La/K, Na/K/Mg/Tm, Na/Dy/K, Na/La/Dy,Na/La/Eu, Na/La/Eu/In, Na/La/K, Na/La/Li/Cs, K/La, K/La/S, K/Na, Li/Cs,Li/Cs/La, Li/Cs/La/Tm, Li/Cs/Sr/Tm, Li/Sr/Cs, Li/Sr/Zn/K, Li/Ga/Cs,Li/K/Sr/La, Li/Na, Li/Na/Rb/Ga, Li/Na/Sr, Li/Na/Sr/La, Li/Sm/Cs,Ba/Sm/Yb/S, Ba/Tm/K/La, Ba/Tm/Zn/K, Cs/K/La, Cs/La/Tm/Na, Cs/Li/K/La,Sm/Li/Sr/Cs, Sr/Cs/La, Sr/Tm/Li/Cs, Zn/K, Zr/Cs/K/La, Rb/Ca/In/Ni,Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca, Li/K, Tm/Lu/Ta/P, Rb/Ca/Dy/P, Mg/La/Yb/Zn,Rb/Sr/Lu, Na/Sr/Lu/Nb, Na/Eu/Hf, Dy/Rb/Gd, Na/Pt/Bi, Rb/Hf, Ca/Cs,Ca/Mg/Na, Hf/Bi, Sr/Sn, Sr/W, Sr/Nb, Zr/W, Y/W, Na/W, Bi/W, Bi/Cs,Bi/Ca, Bi/Sn, Bi/Sb, Ge/Hf, Hf/Sm, Sb/Ag, Sb/Bi, Sb/Au, Sb/Sm, Sb/Sr,Sb/W, Sb/Hf, Sb/Yb, Sb/Sn, Yb/Au, Yb/Ta, Yb/W, Yb/Sr, Yb/Pb, Yb/W,Yb/Ag, Au/Sr, W/Ge, Ta/Hf, W/Au, Ca/W, Au/Re, Sm/Li, La/K, Zn/Cs,Na/K/Mg, Zr/Cs, Ca/Ce, Na/Li/Cs, Li/Sr, Cs/Zn, La/Dy/K, Dy/K, La/Mg,Na/Nd/In/K, In/Sr, Sr/Cs, Rb/Ga/Tm/Cs, Ga/Cs, K/La/Zr/Ag, Lu/Fe, Sr/Tm,La/Dy, Sm/Li/Sr, Mg/K, Li/Rb/Ga, Li/Cs/Tm, Zr/K, Li/Cs, Li/K/La,Ce/Zr/La, Ca/Al/La, Sr/Zn/La, Sr/Cs/Zn, Sm/Cs, In/K, Ho/Cs/Li/La,Cs/La/Na, La/S/Sr, K/La/Zr/Ag, Lu/Tl, Pr/Zn, Rb/Sr/La, Na/Sr/Eu/Ca,K/Cs/Sr/La, Na/Sr/Lu, Sr/Eu/Dy, Lu/Nb, La/Dy/Gd, Na/Mg/Tl/P, Na/Pt,Gd/Li/K, Rb/K/Lu, Sr/La/Dy/S, Na/Ce/Co, Na/Ce, Na/Ga/Gd/Al, Ba/Rh/Ta,Ba/Ta, Na/Al/Bi, Cs/Eu/S, Sm/Tm/Yb/Fe, Sm/Tm/Yb, Hf/Zr/Ta, Rb/Gd/Li/K,Gd/Ho/Al/P, Na/Ca/Lu, Cu/Sn, Ag/Au, Al/Bi, Al/Mo, Al/Nb, Au/Pt, Ga/Bi,Mg/W, Pb/Au, Sn/Mg, Zn/Bi, Gd/Ho, Zr/Bi, Ho/Sr, Gd/Ho/Sr, Ca/Sr,Ca/Sr/W, Sr/Ho/Tm/Na, Na/Zr/Eu/Tm, Sr/Pb, Sr/W/Li, Ca/Sr/W or Sr/Hf. Inone embodiment of the foregoing, nanowires comprise La₂O₃, Nd₂O₃, Yb₂O₃,Eu₂O₃, Sm₂O₃, Ln1_(4-x)Ln2_(x)O₆, La_(4-x)Ln1_(x)O₆, La_(4-x)Nd_(x)O₆,wherein Ln1 and Ln2 are each independently a lanthanide element, whereinLn1 and Ln2 are not the same and x is a number ranging from greater than0 to less than 4, La₃NdO₆, LaNd₃O₆, La_(1.5)Nd_(2.5)O₆,La_(2.5)Nd_(1.5)O₆, La_(3.2)Nd_(0.8)O₆, La_(3.5)Nd_(0.5)O₆,La_(3.8)Nd_(0.2)O₆, Y—La, Zr—La, Pr—La or Ce—La or combinations thereof.

In other embodiments, the nanowires comprise La₂O₃, Yb₂O₃, Eu₂O₃, Sm₂O₃,Y₂O₃, Ce₂O₃, Pr₂O₃, Ln1_(4-x)Ln2_(x)O₆, La_(4-x)Ln1_(x)O₆,La_(4-x)Nd_(x)O₆, wherein L_(n)1 and L_(n)2 are each independently alanthanide element, wherein L_(n)1 and L_(n)2 are not the same and x isa number ranging from greater than 0 to less than 4, La₃NdO₆, LaNd₃O₆,La_(1.5)Nd_(2.5)O₆, La_(2.5)Nd_(1.5)O₆, La_(3.2)Nd_(0.8)O₆,La_(3.5)Nd_(0.5)O₆, La_(3.8)Nd_(0.2)O₆, Y—La, Zr—La, Pr—La or Ce—Ladoped with Sr/Ta, for example in some embodiments the nanowires compriseSr/Ta/La₂O₃, Sr/Ta/Yb₂O₃, Sr/Ta/Eu₂O₃, Sr/Ta/Sm₂O₃, Sr/Ta/La₃NdO₆,Sr/Ta/LaNd₃O₆, Sr/Ta/La_(1.5)Nd_(2.5)O₆, Sr/Ta/La_(2.5)Nd_(1.5)O₆,Sr/Ta/La_(3.2)Nd_(0.8)O₆, Sr/Ta/La_(3.5)Nd_(0.5)O₆,Sr/Ta/La_(3.8)Nd_(0.2)O₆, Sr/Ta/Y—La, Sr/Ta/Zr—La, Sr/Ta/Pr—La orSr/Ta/Ce—La or combinations thereof. In other embodiments, the nanowirescomprise Ln1_(4-x)Ln2_(x)O₆, La_(4-x)Ln1_(x)O₆, La_(4-x)Nd_(x)O₆,wherein Ln1 and Ln2 are each independently a lanthanide element, whereinLn1 and Ln2 are not the same and x is a number ranging from greater than0 to less than 4, La₃NdO₆, LaNd₃O₆, La_(1.5)Nd_(2.5)O₆,La_(2.5)Nd_(1.5)O₆, La_(3.2)Nd_(0.8)O₆, La_(3.5)Nd_(0.5)O₆,La_(3.8)Nd_(0.2)O₆, Y—La, Zr—La, Pr—La or Ce—La doped with Na, Sr, Ca,Yb, Cs or Sb, for example the nanowires may compriseNa/Ln1_(4-x)Ln2_(x)O₆, Sr/Ln1_(4-x)Ln2_(x)O₆, Ca/Ln1_(4-x)Ln2_(x)O₆,Yb/Ln1_(4-x)Ln2_(x)O₆, Cs/Ln1_(4-x)Ln2_(x)O₆, Sb/Ln1_(4-x)Ln2_(x)O₆,Na/La_(4-x)Ln1_(x)O₆, Na/La₃NdO₆, Sr/La_(4-x)Ln1_(x)O₆,Ca/La_(4-x)Ln1_(x)O₆, Yb/La_(4-x)Ln1_(x)O₆, Cs/La_(4-x)Ln1_(x)O₆,Sb/La_(4-x)Ln1_(x)O₆, Na/La_(4-x)Nd_(x)O₆, Sr/La_(4-x)Nd_(x)O₆,Ca/La_(4-x)Nd_(x)O₆, Yb/La_(4-x)Nd_(x)O₆, Cs La_(4-x)Nd_(x)O₆,Sb/La_(4-x)Nd_(x)O₆, Na/LaNd₃O₆, Na/La_(1.5)Nd_(2.5)O₆,Na/La_(2.5)Nd_(1.5)O₆, Na/La_(3.2)Nd_(0.8)O₆, Na/La_(3.5)Nd_(0.5)O₆,Na/La_(3.8)Nd_(0.2)O₆, Na/Y—La, Na/Zr—La, Na/Pr—La, Na/Ce—La,Sr/La₃NdO₆, Sr/LaNd₃O₆, Sr/La_(1.5)Nd_(2.5)O₆, Sr/La_(2.5)Nd_(1.5)O₆,Sr/La_(3.2)Nd_(0.8)O₆, Sr/La_(3.5)Nd_(0.5)O₆, Sr/La_(3.8)Nd_(0.2)O₆,Sr/Y—La, Sr/Zr—La, Sr/Pr—La, Sr/Ce—La, Ca/La₃NdO₆, Ca/LaNd₃O₆,Ca/La_(1.5)Nd_(2.5)O₆, Ca/La_(2.5)Nd_(1.5)O₆, Ca/La_(3.2)Nd_(0.8)O₆,Ca/La_(3.5)Nd_(0.5)O₆, Ca/La_(3.8)Nd_(0.2)O₆, Ca/Y—La, Ca/Zr—La,Ca/Pr—La, Ca/Ce—La, Yb/La₃NdO₆, Yb/LaNd₃O₆, Yb/La_(1.5)Nd_(2.5)O₆,Yb/La_(2.5)Nd_(1.5)O₆, Yb/La_(3.2)Nd_(0.8)O₆, Yb/La_(3.5)Nd_(0.5)O₆,Yb/La_(3.8)Nd_(0.2)O₆, Yb/Y—La, Yb/Zr—La, Yb/Pr—La, Yb/Ce—La,Cs/La₃NdO₆LaNd₃O₆, Cs/La_(1.5)Nd_(2.5)O₆, Cs/La_(2.5)Nd_(1.5)O₆,Cs/La_(3.2)Nd_(0.8)O₆, Cs/La_(3.5)Nd_(0.5)O₆, Cs/La_(3.8)Nd_(0.2)O₆,Cs/Y—La, Cs/Zr—La, Cs/Pr—La, Cs/Ce—La, Sb/La₃NdO₆, Sb/LaNd₃O₆,Sb/La_(1.5)Nd_(2.5)O₆, Sb/La_(2.5)Nd_(1.5)O₆, Sb/La_(3.2)Nd_(0.8)O₆,Sb/La_(3.5)Nd_(0.5)O₆, Sb/La_(3.8)Nd_(0.2)O₆, Sb/Y—La, Sb/Zr—La,Sb/Pr—La, Sb/Ce—La or combinations thereof.

Furthermore, the present inventors have discovered that lanthanideoxides doped with alkali metals and/or alkaline earth metals and atleast one other dopant selected from Groups 3-16 have desirablecatalytic properties and are useful in a variety of catalytic reactions,such as OCM. Accordingly, in one embodiment the nanowire catalystscomprise a lanthanide oxide doped with an alkali metal, an alkalineearth metal or combinations thereof, and at least one other dopant fromgroups 3-16. In some embodiments, the nanowire catalyst comprises alanthanide oxide, an alkali metal dopant and at least one other dopantselected from Groups 3-16. In other embodiments, the nanowire catalystcomprises a lanthanide oxide, an alkaline earth metal dopant and atleast one other dopant selected from Groups 3-16.

In some more specific embodiments of the foregoing, the nanowirecatalyst comprises a lanthanide oxide, a lithium dopant and at least oneother dopant selected from Groups 3-16. In still other embodiments, thenanowire catalyst comprises a lanthanide oxide, a sodium dopant and atleast one other dopant selected from Groups 3-16. In other embodiments,the nanowire catalyst comprises a lanthanide oxide, a potassium dopantand at least one other dopant selected from Groups 3-16. In otherembodiments, the nanowire catalyst comprises a lanthanide oxide, arubidium dopant and at least one other dopant selected from Groups 3-16.In more embodiments, the nanowire catalyst comprises a lanthanide oxide,a caesium dopant and at least one other dopant selected from Groups3-16.

In still other embodiments of the foregoing, the nanowire catalystcomprises a lanthanide oxide, a beryllium dopant and at least one otherdopant selected from Groups 3-16. In other embodiments, the nanowirecatalyst comprises a lanthanide oxide, a magnesium dopant and at leastone other dopant selected from Groups 3-16. In still other embodiments,the nanowire catalyst comprises a lanthanide oxide, a calcium dopant andat least one other dopant selected from Groups 3-16. In moreembodiments, the nanowire catalyst comprises a lanthanide oxide, astrontium dopant and at least one other dopant selected from Groups3-16. In more embodiments, the nanowire catalyst comprises a lanthanideoxide, a barium dopant and at least one other dopant selected fromGroups 3-16.

In some embodiments of the foregoing lanthanide oxide nanowirecatalysts, the catalysts comprise La₂O₃, Nd₂O₃, Yb₂O₃, Eu₂O₃, Sm₂O₃,Ln1_(4-x)Ln2_(x)O₆, La_(4-x)Ln1_(x)O₆, La_(4-x)Nd_(x)O₆, wherein Ln1 andLn2 are each independently a lanthanide element, wherein Ln1 and Ln2 arenot the same and x is a number ranging from greater than 0 to less than4, La₃NdO₆, LaNd₃O₆, La_(1.5)Nd_(2.5)O₆, La_(2.5)Nd_(1.5)O₆,La_(3.2)Nd_(0.8)O₆, La_(3.5)Nd_(0.5)O₆, La_(3.8)Nd_(0.2)O₆, Y—La, Zr—La,Pr—La or Ce—La or combinations thereof. In other various embodiments,the lanthanide oxide nanowire catalyst comprises a C₂ selectivity ofgreater than 50% and a methane conversion of greater than 20% when thelanthanide oxide nanowire catalyst is employed as a heterogenouscatalyst in the oxidative coupling of methane at a temperature of 750°C. or less.

In various embodiments, of any of the above nanowire catalysts, thenanowire catalyst comprises a C₂ selectivity of greater than 50% and amethane conversion of greater than 20% when the nanowire catalyst isemployed as a heterogenous catalyst in the oxidative coupling of methaneat a temperature of 750° C. or less, 700° C. or less, 650° C. or less oreven 600° C. or less.

In more embodiments, of any of the above nanowire catalysts, thenanowire catalyst comprises a C₂ selectivity of greater than 50%,greater than 55%, greater than 60%, greater than 65%, greater than 70%,or even greater than 75%, and a methane conversion of greater than 20%when the nanowire catalyst is employed as a heterogenous catalyst in theoxidative coupling of methane at a temperature of 750° C. or less.

In other embodiments, of any of the above catalysts, the catalystcomprises a C₂ selectivity of greater than 50%, and a methane conversionof greater than 20%, greater than 25%, greater than 30%, greater than35%, greater than 40%, greater than 45%, or even greater than 50% whenthe rare earth oxide catalyst is employed as a heterogenous catalyst inthe oxidative coupling of methane at a temperature of 750° C. or less.In some embodiments of the foregoing, the methan conversion and C2selectivity are calculated based on a single pass basis (i.e., thepercent of methane converted or C2 selectivity upon a single pass overthe catalyst or catalytic bed, etc.)

In some embodiments, the foregoing doped nanowires comprise 1, 2, 3 orfour doping elements. In other embodiments, the nanowires comprise morethan four doping elements, for example, 5, 6, 7, 8, 9, 10 or even moredoping elements. In this regard, each dopant may be present in thenanowires (for example any of the nanowires disclosed in Tables 9-12) inup to 75% by weight. For example, in one embodiment the concentration ofa first doping element ranges from 0.01 to 1% w/w, 1%-5% w/w, 5%-10%w/w. 10%-20% ww, 20%-30% w/w, 30%-40% w/w or 40%-50% w/w, for exampleabout 1% w/w, about 2% w/w, about 3% w/w, about 4% w/w, about 5% w/w,about 6% w/w, about 7% w/w, about 8% w/w, about 9% w/w, about 10% w/w,about 11% w/w, about 12% w/w, about 13% w/w, about 14% w/w, about 15%w/w, about 16% w/w, about 17% w/w, about 18% w/w, about 19% w/w or about20% w/w.

In other embodiments, the concentration of a second doping element (whenpresent) ranges from 0.01% to 1% w/w, 1%-5% w/w, 5%-10% w/w. 10%-20% ww,20%-30% w/w, 30%-40% w/w or 40%-50% w/w, for example about 1% w/w, about2% w/w, about 3% w/w, about 4% w/w, about 5% w/w, about 6% w/w, about 7%w/w, about 8% w/w, about 9% w/w, about 10% w/w, about 11% w/w, about 12%w/w, about 13% w/w, about 14% w/w, about 15% w/w, about 16% w/w, about17% w/w, about 18% w/w, about 19% w/w or about 20% w/w.

In other embodiments, the concentration of a third doping element (whenpresent) ranges from 0.01% to 1% w/w, 1%-5% w/w, 5%-10% w/w. 10%-20% ww,20%-30% w/w, 30%-40% w/w or 40%-50% w/w, for example about 1% w/w, about2% w/w, about 3% w/w, about 4% w/w, about 5% w/w, about 6% w/w, about 7%w/w, about 8% w/w, about 9% w/w, about 10% w/w, about 11% w/w, about 12%w/w, about 13% w/w, about 14% w/w, about 15% w/w, about 16% w/w, about17% w/w, about 18% w/w, about 19% w/w or about 20% w/w. In otherembodiments, the concentration of a fourth doping element (when present)ranges from 0.01% to 1% w/w, 1%-5% w/w, 5%-10% w/w. 10%-20% ww, 20%-30%w/w, 30%-40% w/w or 40%-50% w/w, for example about 1% w/w, about 2% w/w,about 3% w/w, about 4% w/w, about 5% w/w, about 6% w/w, about 7% w/w,about 8% w/w, about 9% w/w, about 10% w/w, about 11% w/w, about 12% w/w,about 13% w/w, about 14% w/w, about 15% w/w, about 16% w/w, about 17%w/w, about 18% w/w, about 19% w/w or about 20% w/w.

In other embodiments, the concentration of the dopant is measured interms of atomic percent (at/at). In some of these embodiments, eachdopant may be present in the nanowires (for example any of the nanowiresdisclosed in Tables 1-12) in up to 75% at/at. For example, in oneembodiment the concentration of a first doping element ranges from 0.01%to 1% at/at, 1%-5% at/at, 5%-10% at/at. 10%-20% at/at, 20%-30% at/at,30%-40% at/at or 40%-50% at/at, for example about 1% at/at, about 2%at/at, about 3% at/at, about 4% at/at, about 5% at/at, about 6% at/at,about 7% at/at, about 8% at/at, about 9% at/at, about 10% at/at, about11% at/at, about 12% at/at, about 13% at/at, about 14% at/at, about 15%at/at, about 16% at/at, about 17% at/at, about 18% at/at, about 19%at/at or about 20% at/at.

In other embodiments, the concentration of a second doping element (whenpresent) ranges from 0.01% to 1% at/at, 1%-5% at/at, 5%-10% at/at.10%-20% ww, 20%-30% at/at, 30%-40% at/at or 40%-50% at/at, for exampleabout 1% at/at, about 2% at/at, about 3% at/at, about 4% at/at, about 5%at/at, about 6% at/at, about 7% at/at, about 8% at/at, about 9% at/at,about 10% at/at, about 11% at/at, about 12% at/at, about 13% at/at,about 14% at/at, about 15% at/at, about 16% at/at, about 17% at/at,about 18% at/at, about 19% at/at or about 20% at/at.

In other embodiments, the concentration of a third doping element (whenpresent) ranges from 0.01% to 1% at/at, 1%-5% at/at, 5%-10% at/at.10%-20% ww, 20%-30% at/at, 30%-40% at/at or 40%-50% at/at, for exampleabout 1% at/at, about 2% at/at, about 3% at/at, about 4% at/at, about 5%at/at, about 6% at/at, about 7% at/at, about 8% at/at, about 9% at/at,about 10% at/at, about 11% at/at, about 12% at/at, about 13% at/at,about 14% at/at, about 15% at/at, about 16% at/at, about 17% at/at,about 18% at/at, about 19% at/at or about 20% at/at.

In other embodiments, the concentration of a fourth doping element (whenpresent) ranges from 0.01% to 1% at/at, 1%-5% at/at, 5%-10% at/at.10%-20% ww, 20%-30% at/at, 30%-40% at/at or 40%-50% at/at, for exampleabout 1% at/at, about 2% at/at, about 3% at/at, about 4% at/at, about 5%at/at, about 6% at/at, about 7% at/at, about 8% at/at, about 9% at/at,about 10% at/at, about 11% at/at, about 12% at/at, about 13% at/at,about 14% at/at, about 15% at/at, about 16% at/at, about 17% at/at,about 18% at/at, about 19% at/at or about 20% at/at.

Accordingly, any of the doped nanowires described above or in Tables1-12, may comprise any of the foregoing doping concentrations.

Furthermore, different catalytic characteristics of the above dopednanowires can be varied or “tuned” based on the method used to preparethem. For example, in one embodiment the above nanowires (and thenanowires of Tables 1-12) are prepared using a biological templatingapproach, for example phage. In other embodiments, the nanowires areprepared via a hydrothermal or sol gel approach (i.e., a non-templatedapproach). Some embodiments for preparing the nanowires (e.g., rareearth nanowires) comprise preparing the nanowires directly from thecorresponding oxide or via a metal hydroxide gel approach. Such methodsare described in more detail herein and other methods are known in theart. In addition, the above dopants may be incorporated either before orafter (or combinations thereof) an optional calcincation step asdescribed herein.

In other embodiments, the nanowires comprise a mixed oxide selected froma Y—La mixed oxide doped with Na. (Y ranges from 5 to 20% of Lamol/mol); a Zr—La mixed oxide doped with Na (Zr ranges from 1 to 5% ofLa mo/mol); a Pr—La mixed oxide doped with a group 1 element (Pr rangesfrom 2 to 6% of La mol/mol); and a Ce—La mixed oxide doped with a group1 element (Ce ranges from 5 to 20% of La mol/mol). As used herein, thenotation “M1-M2”, wherein M1 and M2 are each independently metals refersto a mixed metal oxide comprising the two metals. M1 and M2 may bepresent in equal or different amounts (at/at).

Some embodiments of the metal oxides disclosed herein can be in the formof oxides, oxyhydroxides, hydroxides, oxycarbonates or combinationthereof after being exposed to moisture, carbon dioxide, undergoingincomplete calcination or combination thereof.

It is contemplated that any one or more of the dopants disclosed hereincan be combined with any one of the nanowires disclosed herein to form adoped nanowire comprising one, two, three or more dopants. Tables 1-12below show exemplary doped nanowires in accordance with various specificembodiments. Dopants (Dop) are shown in the horizontal rows and basenanowire catalyst (NW) in the vertical columns for Tables 1-8, anddopants are shown in the vertical columns and base nanowire catalyst inthe horizontal rows for Tables 9-12. The resulting doped catalysts areshown in the intersecting cells in all tables. In some embodiments, thedoped nanowires shown in tables 1-12 are doped with one, two, three ormore additional dopants.

TABLE 1 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS (DOP) Dop NW Li Na KRb Li₂O Li/ Na/ K/ Rb/ Li₂O Li₂O Li₂O Li₂O Na₂O Li/ Na/ K/ Rb/ Na₂O Na₂ONa₂O Na₂O K₂O Li/ Na/ K/ Rb/ K₂O K₂O K₂O K₂O Rb₂O Li/ Na/ K/ Rb/ Rb₂ORb₂O Rb₂O Rb₂O Cs₂O Li/ Na/ K/ Rb/ Cs₂O Cs₂O Cs₂O Cs₂O BeO Li/ Na/ K/Rb/ BeO BeO BeO BeO MgO Li/ Na/ K/ Rb/ MgO MgO MgO MgO CaO Li/ Na/ K/Rb/ CaO CaO CaO CaO SrO Li/ Na/ K/ Rb/ SrO SrO SrO SrO BaO Li/ Na/ K/Rb/ BaO BaO BaO BaO Sc₂O₃ Li/ Na/ K/ Rb/ Sc₂O₃ Sc₂O₃ Sc₂O₃ Sc₂O₃ Y₂O₃Li/ Na/ K/ Rb/ Y₂O₃ Y₂O₃ Y₂O₃ Y₂O₃ La₂O₃ Li/ Na/ K/ Rb/ La₂O₃ La₂O₃La₂O₃ La₂O₃ CeO₂ Li/ Na/ K/ Rb/ CeO₂ CeO₂ CeO₂ CeO₂ Ce₂O₃ Li/ Na/ K/ Rb/Ce₂O₃ Ce₂O₃ Ce₂O₃ Ce₂O₃ Pr₂O₃ Li/ Na/ K/ Rb/ Pr₂O₃ Pr₂O₃ Pr₂O₃ Pr₂O₃Nd₂O₃ Li/ Na/ K/ Rb/ Nd₂O₃ Nd₂O₃ Nd₂O₃ Nd₂O₃ Sm₂O₃ Li/ Na/ K/ Rb/ Sm₂O₃Sm₂O₃ Sm₂O₃ Sm₂O₃ Eu₂O₃ Li/ Na/ K/ Rb/ Eu₂O₃ Eu₂O₃ Eu₂O₃ Eu₂O₃ Gd₂O₃ Li/Na/ K/ Rb/ Gd₂O₃ Gd₂O₃ Gd₂O₃ Gd₂O₃ Tb₂O₃ Li/ Na/ K/ Rb/ Tb₂O₃ Tb₂O₃Tb₂O₃ Tb₂O₃ TbO₂ Li/ Na/ K/ Rb/ TbO₂ TbO₂ TbO₂ TbO₂ Tb₆O₁₁ Li/ Na/ K/Rb/ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Dy₂O₃ Li/ Na/ K/ Rb/ Dy₂O₃ Dy₂O₃ Dy₂O₃Dy₂O₃ Ho₂O₃ Li/ Na/ K/ Rb/ Ho₂O₃ Ho₂O₃ Ho₂O₃ Ho₂O₃ Er₂O₃ Li/ Na/ K/ Rb/Er₂O₃ Er₂O₃ Er₂O₃ Er₂O₃ Tm₂O₃ Li/ Na/ K/ Rb/ Tm₂O₃ Tm₂O₃ Tm₂O₃ Tm₂O₃Yb₂O₃ Li/ Na/ K/ Rb/ Yb₂O₃ Yb₂O₃ Yb₂O₃ Yb₂O₃ Lu₂O₃ Li/ Na/ K/ Rb/ Lu₂O₃Lu₂O₃ Lu₂O₃ Lu₂O₃ Ac₂O₃ Li/ Na/ K/ Rb/ Ac₂O₃ Ac₂O₃ Ac₂O₃ Ac₂O₃ Th₂O₃ Li/Na/ K/ Rb/ Th₂O₃ Th₂O₃ Th₂O₃ Th₂O₃ ThO₂ Li/ Na/ K/ Rb/ ThO₂ ThO₂ ThO₂ThO₂ Pa₂O₃ Li/ Na/ K/ Rb/ Pa₂O₃ Pa₂O₃ Pa₂O₃ Pa₂O₃ PaO₂ Li/ Na/ K/ Rb/PaO₂ PaO₂ PaO₂ PaO₂ TiO₂ Li/ Na/ K/ Rb/ TiO₂ TiO₂ TiO₂ TiO₂ TiO Li/ Na/K/ Rb/ TiO TiO TiO TiO Ti₂O₃ Li/ Na/ K/ Rb/ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₃OLi/ Na/ K/ Rb/ Ti₃O Ti₃O Ti₃O Ti₃O Ti₂O Li/ Na/ K/ Rb/ Ti₂O Ti₂O Ti₂OTi₂O Ti₃O₅ Li/ Na/ K/ Rb/ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₄O₇ Li/ Na/ K/ Rb/Ti₄O₇ Ti₄O₇ Ti₄O₇ Ti₄O₇ ZrO₂ Li/ Na/ K/ Rb/ ZrO₂ ZrO₂ ZrO₂ ZrO₂ HfO₂ Li/Na/ K/ Rb/ HfO₂ HfO₂ HfO₂ HfO₂ VO Li/ Na/ K/ Rb/ VO VO VO VO V₂O₃ Li/Na/ K/ Rb/ V₂O₃ V₂O₃ V₂O₃ V₂O₃ VO₂ Li/ Na/ K/ Rb/ VO₂ VO₂ VO₂ VO₂ V₂O₅Li/ Na/ K/ Rb/ V₂O₅ V₂O₅ V₂O₅ V₂O₅ V₃O₇ Li/ Na/ K/ Rb/ V₃O₇ V₃O₇ V₃O₇V₃O₇ V₄O₉ Li/ Na/ K/ Rb/ V₄O₉ V₄O₉ V₄O₉ V₄O₉ V₆O₁₃ Li/ Na/ K/ Rb/ V₆O₁₃V₆O₁₃ V₆O₁₃ V₆O₁₃ NbO Li/ Na/ K/ Rb/ NbO NbO NbO NbO NbO₂ Li/ Na/ K/ Rb/NbO₂ NbO₂ NbO₂ NbO₂ Nb₂O₅ Li/ Na/ K/ Rb/ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₈O₁₉Li/ Na/ K/ Rb/ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₁₆O₃₈ Li/ Na/ K/ Rb/Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₂O₂₉ Li/ Na/ K/ Rb/ Nb₁₂O₂₉ Nb₁₂O₂₉Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₄₇O₁₁₆ Li/ Na/ K/ Rb/ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆Nb₄₇O₁₁₆ Ta₂O₅ Li/ Na/ K/ Rb/ Ta₂O₅ Ta₂O₅ Ta₂O₅ Ta₂O₅ CrO Li/ Na/ K/ Rb/CrO CrO CrO CrO Cr₂O₃ Li/ Na/ K/ Rb/ Cr₂O₃ Cr₂O₃ Cr₂O₃ Cr₂O₃ CrO₂ Li/Na/ K/ Rb/ CrO₂ CrO₂ CrO₂ CrO₂ CrO₃ Li/ Na/ K/ Rb/ CrO₃ CrO₃ CrO₃ CrO₃Cr₈O₂₁ Li/ Na/ K/ Rb/ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ MoO₂ Li/ Na/ K/ Rb/MoO₂ MoO₂ MoO₂ MoO₂ MoO₃ Li/ Na/ K/ Rb/ MoO₃ MoO₃ MoO₃ MoO₃ W₂O₃ Li/ Na/K/ Rb/ W₂O₃ W₂O₃ W₂O₃ W₂O₃ WoO₂ Li/ Na/ K/ Rb/ WoO₂ WoO₂ WoO₂ WoO₂ WoO₃Li/ Na/ K/ Rb/ WoO₃ WoO₃ WoO₃ WoO₃ MnO Li/ Na/ K/ Rb/ MnO MnO MnO MnOMn/Mg/O Li/ Na/ K/ Rb/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn₃O₄ Li/ Na/ K/Rb/ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₂O₃ Li/ Na/ K/ Rb/ Mn₂O₃ Mn₂O₃ Mn₂O₃ Mn₂O₃MnO₂ Li/ Na/ K/ Rb/ MnO₂ MnO₂ MnO₂ MnO₂ Mn₂O₇ Li/ Na/ K/ Rb/ Mn₂O₇ Mn₂O₇Mn₂O₇ Mn₂O₇ ReO₂ Li/ Na/ K/ Rb/ ReO₂ ReO₂ ReO₂ ReO₂ ReO₃ Li/ Na/ K/ Rb/ReO₃ ReO₃ ReO₃ ReO₃ Re₂O₇ Li/ Na/ K/ Rb/ Re₂O₇ Re₂O₇ Re₂O₇ Re₂O₇Mg₃Mn₃—B₂O₁₀ Li/ Na/ K/ Rb/ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀Mg₃Mn₃—B₂O₁₀ Mg₃(BO₃)₂ Li/ Na/ K/ Rb/ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂Mg₃(BO₃)₂ NaWO₄ Li/ Na/ K/ Rb/ NaWO₄ NaWO₄ NaWO₄ NaWO₄ Mg₆MnO₈ Li/ Na/K/ Rb/ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ (Li,Mg)₆—MnO₈ Li/ Na/ K/ Rb/(Li,Mg)₆—MnO₈ (Li,Mg)₆—MnO₈ (Li,Mg)₆—MnO₈ (Li,Mg)₆—MnO₈ Mn₂O₄ Li/ Na/ K/Rb/ Mn₂O₄ Mn₂O₄ Mn₂O₄ Mn₂O₄ Na₄P₂O₇ Li/ Na/ K/ Rb/ Na₄P₂O₇ Na₄P₂O₇Na₄P₂O₇ Na₄P₂O₇ Mo₂O₈ Li/ Na/ K/ Rb/ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mn₃O₄/ Li/Na/ K/ Rb/ WO₄ Mn₃O₄/ Mn₃O₄/ Mn₃O₄/ Mn₃O₄/ WO₄ WO₄ WO₄ WO₄ Na₂WO₄ Li/Na/ K/ Rb/ Na₂WO₄ Na₂WO₄ Na₂WO₄ Na₂WO₄ Zr₂Mo₂O₈ Li/ Na/ K/ Rb/ Zr₂Mo₂O₈Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ NaMnO₄—/ Li/ Na/ K/ Rb/ MgO NaMnO₄—/ NaMnO₄—/NaMnO₄—/ NaMnO₄—/ MgO MgO MgO MgO Na₁₀Mn—W₅O₁₇ Li/ Na/ K/ Rb/Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ La₃NdO₆ Li/ Na/ K/Rb/ La₃NdO₆ La₃NdO₆ La₃NdO₆ La₃NdO₆ LaNd₃O₆ Li/ Na/ K/ Rb/ LaNd₃O₆LaNd₃O₆ LaNd₃O₆ LaNd₃O₆ La_(1,5)Nd_(2,5)O₆ Li/ Na/ K/ Rb/La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆La_(1,5)Nd_(2,5)O₆ La_(2,5)Nd_(1,5)O₆ Li/ Na/ K/ Rb/ La_(2,5)Nd_(1,5)O₆La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆La_(3,2)Nd_(0,8)O₆ Li/ Na/ K/ Rb/ La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆ La_(3,5)Nd_(0,5)O₆ Li/ Na/ K/ Rb/La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆La_(3,5)Nd_(0,5)O₆ La_(3,8)Nd_(0,2)O₆ Li/ Na/ K/ Rb/ La_(3,8)Nd_(0,2)O₆La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆ Y—La Li/ Na/ K/Rb/ Y—La Y—La Y—La Y—La Zr—La Li/ Na/ K/ Rb/ Zr—La Zr—La Zr—La Zr—LaPr—La Li/ Na/ K/ Rb/ Pr—La Pr—La Pr—La Pr—La Ce—La Li/ Na/ K/ Rb/ Ce—LaCe—La Ce—La Ce—La Dop NW Cs Be Mg Ca Li₂O Cs/ Be/ Mg/ Ca/ Li₂O Li₂O Li₂OLi₂O Na₂O Cs/ Be/ Mg/ Ca/ Na₂O Na₂O Na₂O Na₂O K₂O Cs/ Be/ Mg/ Ca/ K₂OK₂O K₂O K₂O Rb₂O Cs/ Be/ Mg/ Ca/ Rb₂O Rb₂O Rb₂O Rb₂O Cs₂O Cs/ Be/ Mg/Ca/ Cs₂O Cs₂O Cs₂O Cs₂O BeO Cs/ Be/ Mg/ Ca/ BeO BeO BeO BeO MgO Cs/ Be/Mg/ Ca/ MgO MgO MgO MgO CaO Cs/ Be/ Mg/ Ca/ CaO CaO CaO CaO SrO Cs/ Be/Mg/ Ca/ SrO SrO SrO SrO BaO Cs/ Be/ Mg/ Ca/ BaO BaO BaO BaO Sc₂O₃ Cs/Be/ Mg/ Ca/ Sc₂O₃ Sc₂O₃ Sc₂O₃ Sc₂O₃ Y₂O₃ Cs/ Be/ Mg/ Ca/ Y₂O₃ Y₂O₃ Y₂O₃Y₂O₃ La₂O₃ Cs/ Be/ Mg/ Ca/ La₂O₃ La₂O₃ La₂O₃ La₂O₃ CeO₂ Cs/ Be/ Mg/ Ca/CeO₂ CeO₂ CeO₂ CeO₂ Ce₂O₃ Cs/ Be/ Mg/ Ca/ Ce₂O₃ Ce₂O₃ Ce₂O₃ Ce₂O₃ Pr₂O₃Cs/ Be/ Mg/ Ca/ Pr₂O₃ Pr₂O₃ Pr₂O₃ Pr₂O₃ Nd₂O₃ Cs/ Be/ Mg/ Ca/ Nd₂O₃Nd₂O₃ Nd₂O₃ Nd₂O₃ Sm₂O₃ Cs/ Be/ Mg/ Ca/ Sm₂O₃ Sm₂O₃ Sm₂O₃ Sm₂O₃ Eu₂O₃Cs/ Be/ Mg/ Ca/ Eu₂O₃ Eu₂O₃ Eu₂O₃ Eu₂O₃ Gd₂O₃ Cs/ Be/ Mg/ Ca/ Gd₂O₃Gd₂O₃ Gd₂O₃ Gd₂O₃ Tb₂O₃ Cs/ Be/ Mg/ Ca/ Tb₂O₃ Tb₂O₃ Tb₂O₃ Tb₂O₃ TbO₂ Cs/Be/ Mg/ Ca/ TbO₂ TbO₂ TbO₂ TbO₂ Tb₆O₁₁ Cs/ Be/ Mg/ Ca/ Tb₆O₁₁ Tb₆O₁₁Tb₆O₁₁ Tb₆O₁₁ Dy₂O₃ Cs/ Be/ Mg/ Ca/ Dy₂O₃ Dy₂O₃ Dy₂O₃ Dy₂O₃ Ho₂O₃ Cs/Be/ Mg/ Ca/ Ho₂O₃ Ho₂O₃ Ho₂O₃ Ho₂O₃ Er₂O₃ Cs/ Be/ Mg/ Ca/ Er₂O₃ Er₂O₃Er₂O₃ Er₂O₃ Tm₂O₃ Cs/ Be/ Mg/ Ca/ Tm₂O₃ Tm₂O₃ Tm₂O₃ Tm₂O₃ Yb₂O₃ Cs/ Be/Mg/ Ca/ Yb₂O₃ Yb₂O₃ Yb₂O₃ Yb₂O₃ Lu₂O₃ Cs/ Be/ Mg/ Ca/ Lu₂O₃ Lu₂O₃ Lu₂O₃Lu₂O₃ Ac₂O₃ Cs/ Be/ Mg/ Ca/ Ac₂O₃ Ac₂O₃ Ac₂O₃ Ac₂O₃ Th₂O₃ Cs/ Be/ Mg/Ca/ Th₂O₃ Th₂O₃ Th₂O₃ Th₂O₃ ThO₂ Cs/ Be/ Mg/ Ca/ ThO₂ ThO₂ ThO₂ ThO₂Pa₂O₃ Cs/ Be/ Mg/ Ca/ Pa₂O₃ Pa₂O₃ Pa₂O₃ Pa₂O₃ PaO₂ Cs/ Be/ Mg/ Ca/ PaO₂PaO₂ PaO₂ PaO₂ TiO₂ Cs/ Be/ Mg/ Ca/ TiO₂ TiO₂ TiO₂ TiO₂ TiO Cs/ Be/ Mg/Ca/ TiO TiO TiO TiO Ti₂O₃ Cs/ Be/ Mg/ Ca/ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₃OCs/ Be/ Mg/ Ca/ Ti₃O Ti₃O Ti₃O Ti₃O Ti₂O Cs/ Be/ Mg/ Ca/ Ti₂O Ti₂O Ti₂OTi₂O Ti₃O₅ Cs/ Be/ Mg/ Ca/ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₄O₇ Cs/ Be/ Mg/ Ca/Ti₄O₇ Ti₄O₇ Ti₄O₇ Ti₄O₇ ZrO₂ Cs/ Be/ Mg/ Ca/ ZrO₂ ZrO₂ ZrO₂ ZrO₂ HfO₂Cs/ Be/ Mg/ Ca/ HfO₂ HfO₂ HfO₂ HfO₂ VO Cs/ Be/ Mg/ Ca/ VO VO VO VO V₂O₃Cs/ Be/ Mg/ Ca/ V₂O₃ V₂O₃ V₂O₃ V₂O₃ VO₂ Cs/ Be/ Mg/ Ca/ VO₂ VO₂ VO₂ VO₂V₂O₅ Cs/ Be/ Mg/ Ca/ V₂O₅ V₂O₅ V₂O₅ V₂O₅ V₃O₇ Cs/ Be/ Mg/ Ca/ V₃O₇ V₃O₇V₃O₇ V₃O₇ V₄O₉ Cs/ Be/ Mg/ Ca/ V₄O₉ V₄O₉ V₄O₉ V₄O₉ V₆O₁₃ Cs/ Be/ Mg/ Ca/V₆O₁₃ V₆O₁₃ V₆O₁₃ V₆O₁₃ NbO Cs/ Be/ Mg/ Ca/ NbO NbO NbO NbO NbO₂ Cs/ Be/Mg/ Ca/ NbO₂ NbO₂ NbO₂ NbO₂ Nb₂O₅ Cs/ Be/ Mg/ Ca/ Nb₂O₅ Nb₂O₅ Nb₂O₅Nb₂O₅ Nb₈O₁₉ Cs/ Be/ Mg/ Ca/ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₁₆O₃₈ Cs/ Be/Mg/ Ca/ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₂O₂₉ Cs/ Be/ Mg/ Ca/ Nb₁₂O₂₉Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₄₇O₁₁₆ Cs/ Be/ Mg/ Ca/ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Ta₂O₅ Cs/ Be/ Mg/ Ca/ Ta₂O₅ Ta₂O₅ Ta₂O₅ Ta₂O₅ CrO Cs/Be/ Mg/ Ca/ CrO CrO CrO CrO Cr₂O₃ Cs/ Be/ Mg/ Ca/ Cr₂O₃ Cr₂O₃ Cr₂O₃Cr₂O₃ CrO₂ Cs/ Be/ Mg/ Ca/ CrO₂ CrO₂ CrO₂ CrO₂ CrO₃ Cs/ Be/ Mg/ Ca/ CrO₃CrO₃ CrO₃ CrO₃ Cr₈O₂₁ Cs/ Be/ Mg/ Ca/ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ MoO₂Cs/ Be/ Mg/ Ca/ MoO₂ MoO₂ MoO₂ MoO₂ MoO₃ Cs/ Be/ Mg/ Ca/ MoO₃ MoO₃ MoO₃MoO₃ W₂O₃ Cs/ Be/ Mg/ Ca/ W₂O₃ W₂O₃ W₂O₃ W₂O₃ WoO₂ Cs/ Be/ Mg/ Ca/ WoO₂WoO₂ WoO₂ WoO₂ WoO₃ Cs/ Be/ Mg/ Ca/ WoO₃ WoO₃ WoO₃ WoO₃ MnO Cs/ Be/ Mg/Ca/ MnO MnO MnO MnO Mn/Mg/O Cs/ Be/ Mg/ Ca/ Mn/Mg/O Mn/Mg/O Mn/Mg/OMn/Mg/O Mn₃O₄ Cs/ Be/ Mg/ Ca/ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₂O₃ Cs/ Be/ Mg/Ca/ Mn₂O₃ Mn₂O₃ Mn₂O₃ Mn₂O₃ MnO₂ Cs/ Be/ Mg/ Ca/ MnO₂ MnO₂ MnO₂ MnO₂Mn₂O₇ Cs/ Be/ Mg/ Ca/ Mn₂O₇ Mn₂O₇ Mn₂O₇ Mn₂O₇ ReO₂ Cs/ Be/ Mg/ Ca/ ReO₂ReO₂ ReO₂ ReO₂ ReO₃ Cs/ Be/ Mg/ Ca/ ReO₃ ReO₃ ReO₃ ReO₃ Re₂O₇ Cs/ Be/Mg/ Ca/ Re₂O₇ Re₂O₇ Re₂O₇ Re₂O₇ Mg₃Mn₃—B₂O₁₀ Cs/ Be/ Mg/ Ca/Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀ Mg₃(BO₃)₂ Cs/ Be/Mg/ Ca/ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂ NaWO₄ Cs/ Be/ Mg/ Ca/NaWO₄ NaWO₄ NaWO₄ NaWO₄ Mg₆MnO₈ Cs/ Be/ Mg/ Ca/ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈Mg₆MnO₈ (Li,Mg)₆—MnO₈ Cs/ Be/ Mg/ Ca/ (Li,Mg)₆—MnO₈ (Li,Mg)₆—MnO₈(Li,Mg)₆—MnO₈ (Li,Mg)₆—MnO₈ Mn₂O₄ Cs/ Be/ Mg/ Ca/ Mn₂O₄ Mn₂O₄ Mn₂O₄Mn₂O₄ Na₄P₂O₇ Cs/ Be/ Mg/ Ca/ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Mo₂O₈ Cs/Be/ Mg/ Ca/ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mn₃O₄/ Cs/ Be/ Mg/ Ca/ WO₄ Mn₃O₄/Mn₃O₄/ Mn₃O₄/ Mn₃O₄/ WO₄ WO₄ WO₄ WO₄ Na₂WO₄ Cs/ Be/ Mg/ Ca/ Na₂WO₄Na₂WO₄ Na₂WO₄ Na₂WO₄ Zr₂Mo₂O₈ Cs/ Be/ Mg/ Ca/ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈Zr₂Mo₂O₈ NaMnO₄—/ Cs/ Be/ Mg/ Ca/ MgO NaMnO₄—/ NaMnO₄—/ NaMnO₄—/NaMnO₄—/ MgO MgO MgO MgO Na₁₀Mn—W₅O₁₇ Cs/ Be/ Mg/ Ca/ Na₁₀Mn—W₅O₁₇Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ La₃NdO₆ Cs/ Be/ Mg/ Ca/ La₃NdO₆La₃NdO₆ La₃NdO₆ La₃NdO₆ LaNd₃O₆ Cs/ Be/ Mg/ Ca/ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆LaNd₃O₆ La_(1,5)Nd_(2,5)O₆ Cs/ Be/ Mg/ Ca/ La_(1,5)Nd_(2,5)O₆La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆La_(2,5)Nd_(1,5)O₆ Cs/ Be/ Mg/ Ca/ La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆ La_(3,2)Nd_(0,8)O₆ Cs/ Be/ Mg/ Ca/La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆La_(3,2)Nd_(0,8)O₆ La_(3,5)Nd_(0,5)O₆ Cs/ Be/ Mg/ Ca/ La_(3,5)Nd_(0,5)O₆La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆La_(3,8)Nd_(0,2)O₆ Cs/ Be/ Mg/ Ca/ La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆ Y—La Cs/ Be/ Mg/ Ca/ Y—La Y—LaY—La Y—La Zr—La Cs/ Be/ Mg/ Ca/ Zr—La Zr—La Zr—La Zr—La Pr—La Cs/ Be/Mg/ Ca/ Pr—La Pr—La Pr—La Pr—La Ce—La Cs/ Be/ Mg/ Ca/ Ce—La Ce—La Ce—LaCe—La

TABLE 2 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS (DOP) Dop NW Sr Ba BP Li₂O Sr/ Ba/ B/ P/ Li₂O Li₂O Li₂O Li₂O Na₂O Sr/ Ba/ B/ P/ Na₂O Na₂ONa₂O Na₂O K₂O Sr/ Ba/ B/ P/ K₂O K₂O K₂O K₂O Rb₂O Sr/ Ba/ B/ P/ Rb₂O Rb₂ORb₂O Rb₂O Cs₂O Sr/ Ba/ B/ P/ Cs₂O Cs₂O Cs₂O Cs₂O BeO Sr/ Ba/ B/ P/ BeOBeO BeO BeO MgO Sr/ Ba/ B/ P/ MgO MgO MgO MgO CaO Sr/ Ba/ B/ P/ CaO CaOCaO CaO SrO Sr/ Ba/ B/ P/ SrO SrO SrO SrO BaO Sr/ Ba/ B/ P/ BaO BaO BaOBaO Sc₂O₃ Sr/ Ba/ B/ P/ Sc₂O₃ Sc₂O₃ Sc₂O₃ Sc₂O₃ Y₂O₃ Sr/ Ba/ B/ P/ Y₂O₃Y₂O₃ Y₂O₃ Y₂O₃ La₂O₃ Sr/ Ba/ B/ P/ La₂O₃ La₂O₃ La₂O₃ La₂O₃ CeO₂ Sr/ Ba/B/ P/ CeO₂ CeO₂ CeO₂ CeO₂ Ce₂O₃ Sr/ Ba/ B/ P/ Ce₂O₃ Ce₂O₃ Ce₂O₃ Ce₂O₃Pr₂O₃ Sr/ Ba/ B/ P/ Pr₂O₃ Pr₂O₃ Pr₂O₃ Pr₂O₃ Nd₂O₃ Sr/ Ba/ B/ P/ Nd₂O₃Nd₂O₃ Nd₂O₃ Nd₂O₃ Sm₂O₃ Sr/ Ba/ B/ P/ Sm₂O₃ Sm₂O₃ Sm₂O₃ Sm₂O₃ Eu₂O₃ Sr/Ba/ B/ P/ Eu₂O₃ Eu₂O₃ Eu₂O₃ Eu₂O₃ Gd₂O₃ Sr/ Ba/ B/ P/ Gd₂O₃ Gd₂O₃ Gd₂O₃Gd₂O₃ Tb₂O₃ Sr/ Ba/ B/ P/ Tb₂O₃ Tb₂O₃ Tb₂O₃ Tb₂O₃ TbO₂ Sr/ Ba/ B/ P/TbO₂ TbO₂ TbO₂ TbO₂ Tb₆O₁₁ Sr/ Ba/ B/ P/ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁Dy₂O₃ Sr/ Ba/ B/ P/ Dy₂O₃ Dy₂O₃ Dy₂O₃ Dy₂O₃ Ho₂O₃ Sr/ Ba/ B/ P/ Ho₂O₃Ho₂O₃ Ho₂O₃ Ho₂O₃ Er₂O₃ Sr/ Ba/ B/ P/ Er₂O₃ Er₂O₃ Er₂O₃ Er₂O₃ Tm₂O₃ Sr/Ba/ B/ P/ Tm₂O₃ Tm₂O₃ Tm₂O₃ Tm₂O₃ Yb₂O₃ Sr/ Ba/ B/ P/ Yb₂O₃ Yb₂O₃ Yb₂O₃Yb₂O₃ Lu₂O₃ Sr/ Ba/ B/ P/ Lu₂O₃ Lu₂O₃ Lu₂O₃ Lu₂O₃ Ac₂O₃ Sr/ Ba/ B/ P/Ac₂O₃ Ac₂O₃ Ac₂O₃ Ac₂O₃ Th₂O₃ Sr/ Ba/ B/ P/ Th₂O₃ Th₂O₃ Th₂O₃ Th₂O₃ ThO₂Sr/ Ba/ B/ P/ ThO₂ ThO₂ ThO₂ ThO₂ Pa₂O₃ Sr/ Ba/ B/ P/ Pa₂O₃ Pa₂O₃ Pa₂O₃Pa₂O₃ PaO₂ Sr/ Ba/ B/ P/ PaO₂ PaO₂ PaO₂ PaO₂ TiO₂ Sr/ Ba/ B/ P/ TiO₂TiO₂ TiO₂ TiO₂ TiO Sr/ Ba/ B/ P/ TiO TiO TiO TiO Ti₂O₃ Sr/ Ba/ B/ P/Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₃O Sr/ Ba/ B/ P/ Ti₃O Ti₃O Ti₃O Ti₃O Ti₂O Sr/Ba/ B/ P/ Ti₂O Ti₂O Ti₂O Ti₂O Ti₃O₅ Sr/ Ba/ B/ P/ Ti₃O₅ Ti₃O₅ Ti₃O₅Ti₃O₅ Ti₄O₇ Sr/ Ba/ B/ P/ Ti₄O₇ Ti₄O₇ Ti₄O₇ Ti₄O₇ ZrO₂ Sr/ Ba/ B/ P/ZrO₂ ZrO₂ ZrO₂ ZrO₂ HfO₂ Sr/ Ba/ B/ P/ HfO₂ HfO₂ HfO₂ HfO₂ VO Sr/ Ba/ B/P/ VO VO VO VO V₂O₃ Sr/ Ba/ B/ P/ V₂O₃ V₂O₃ V₂O₃ V₂O₃ VO₂ Sr/ Ba/ B/ P/VO₂ VO₂ VO₂ VO₂ V₂O₅ Sr/ Ba/ B/ P/ V₂O₅ V₂O₅ V₂O₅ V₂O₅ V₃O₇ Sr/ Ba/ B/P/ V₃O₇ V₃O₇ V₃O₇ V₃O₇ V₄O₉ Sr/ Ba/ B/ P/ V₄O₉ V₄O₉ V₄O₉ V₄O₉ V₆O₁₃ Sr/Ba/ B/ P/ V₆O₁₃ V₆O₁₃ V₆O₁₃ V₆O₁₃ NbO Sr/ Ba/ B/ P/ NbO NbO NbO NbO NbO₂Sr/ Ba/ B/ P/ NbO₂ NbO₂ NbO₂ NbO₂ Nb₂O₅ Sr/ Ba/ B/ P/ Nb₂O₅ Nb₂O₅ Nb₂O₅Nb₂O₅ Nb₈O₁₉ Sr/ Ba/ B/ P/ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₁₆O₃₈ Sr/ Ba/B/ P/ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₂O₂₉ Sr/ Ba/ B/ P/ Nb₁₂O₂₉Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₄₇O₁₁₆ Sr/ Ba/ B/ P/ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Ta₂O₅ Sr/ Ba/ B/ P/ Ta₂O₅ Ta₂O₅ Ta₂O₅ Ta₂O₅ CrO Sr/Ba/ B/ P/ CrO CrO CrO CrO Cr₂O₃ Sr/ Ba/ B/ P/ Cr₂O₃ Cr₂O₃ Cr₂O₃ Cr₂O₃CrO₂ Sr/ Ba/ B/ P/ CrO₂ CrO₂ CrO₂ CrO₂ CrO₃ Sr/ Ba/ B/ P/ CrO₃ CrO₃ CrO₃CrO₃ Cr₈O₂₁ Sr/ Ba/ B/ P/ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ MoO₂ Sr/ Ba/ B/ P/MoO₂ MoO₂ MoO₂ MoO₂ MoO₃ Sr/ Ba/ B/ P/ MoO₃ MoO₃ MoO₃ MoO₃ W₂O₃ Sr/ Ba/B/ P/ W₂O₃ W₂O₃ W₂O₃ W₂O₃ WoO₂ Sr/ Ba/ B/ P/ WoO₂ WoO₂ WoO₂ WoO₂ WoO₃Sr/ Ba/ B/ P/ WoO₃ WoO₃ WoO₃ WoO₃ MnO Sr/ Ba/ B/ P/ MnO MnO MnO MnOMn/Mg/O Sr/ Ba/ B/ P/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn₃O₄ Sr/ Ba/ B/P/ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₂O₃ Sr/ Ba/ B/ P/ Mn₂O₃ Mn₂O₃ Mn₂O₃ Mn₂O₃MnO₂ Sr/ Ba/ B/ P/ MnO₂ MnO₂ MnO₂ MnO₂ Mn₂O₇ Sr/ Ba/ B/ P/ Mn₂O₇ Mn₂O₇Mn₂O₇ Mn₂O₇ ReO₂ Sr/ Ba/ B/ P/ ReO₂ ReO₂ ReO₂ ReO₂ ReO₃ Sr/ Ba/ B/ P/ReO₃ ReO₃ ReO₃ ReO₃ Re₂O₇ Sr/ Ba/ B/ P/ Re₂O₇ Re₂O₇ Re₂O₇ Re₂O₇Mg₃Mn₃—B₂O₁₀ Sr/ Ba/ B/ P/ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀Mg₃Mn₃—B₂O₁₀ Mg₃(BO₃)₂ Sr/ Ba/ B/ P/ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂Mg₃(BO₃)₂ NaWO₄ Sr/ Ba/ B/ P/ NaWO₄ NaWO₄ NaWO₄ NaWO₄ Mg₆MnO₈ Sr/ Ba/ B/P/ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ (Li,Mg)₆MnO₈ Sr/ Ba/ B/ P/(Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ Mn₂O₄ Sr/ Ba/ B/ P/Mn₂O₄ Mn₂O₄ Mn₂O₄ Mn₂O₄ Na₄P₂O₇ Sr/ Ba/ B/ P/ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇Na₄P₂O₇ Mo₂O₈ Sr/ Ba/ B/ P/ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mn₃O₄/WO₄ Sr/ Ba/ B/P/ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Na₂WO₄ Sr/ Ba/ B/ P/ Na₂WO₄Na₂WO₄ Na₂WO₄ Na₂WO₄ Zr₂Mo₂O₈ Sr/ Ba/ B/ P/ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈Zr₂Mo₂O₈ NaMnO₄/MgO Sr/ Ba/ B/ P/ NaMnO₄/MgO NaMnO₄/MgO NaMnO₄/MgONaMnO₄/MgO Na₁₀Mn—W₅O₁₇ Sr/ Ba/ B/ P/ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ La₃NdO₆ Sr/ Ba/ B/ P/ La₃NdO₆ La₃NdO₆ La₃NdO₆La₃NdO₆ LaNd₃O₆ Sr/ Ba/ B/ P/ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆La_(1,5)Nd_(2,5)O₆ Sr/ Ba/ B/ P/ La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆ La_(2,5)Nd_(1,5)O₆ Sr/ Ba/ B/ P/La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆La_(2,5)Nd_(1,5)O₆ La_(3,2)Nd_(0,8)O₆ Sr/ Ba/ B/ P/ La_(3,2)Nd_(0,8)O₆La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆La_(3,5)Nd_(0,5)O₆ Sr/ Ba/ B/ P/ La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆ La_(3,8)Nd_(0,2)O₆ Sr/ Ba/ B/ P/La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆La_(3,8)Nd_(0,2)O₆ Y—La Sr/ Ba/ B/ P/ Y—La Y—La Y—La Y—La Zr—La Sr/ Ba/B/ P/ Zr—La Zr—La Zr—La Zr—La Pr—La Sr/ Ba/ B/ P/ Pr—La Pr—La Pr—LaPr—La Ce—La Sr/ Ba/ B/ P/ Ce—La Ce—La Ce—La Ce—La Dop NW S F Cl Li₂O S/F/ Cl/ Li₂O Li₂O Li₂O Na₂O S/ F/ Cl/ Na₂O Na₂O Na₂O K₂O S/ F/ Cl/ K₂OK₂O K₂O Rb₂O S/ F/ Cl/ Rb₂O Rb₂O Rb₂O Cs₂O S/ F/ Cl/ Cs₂O Cs₂O Cs₂O BeOS/ F/ Cl/ BeO BeO BeO MgO S/ F/ Cl/ MgO MgO MgO CaO S/ F/ Cl/ CaO CaOCaO SrO S/ F/ Cl/ SrO SrO SrO BaO S/ F/ Cl/ BaO BaO BaO Sc₂O₃ S/ F/ Cl/Sc₂O₃ Sc₂O₃ Sc₂O₃ Y₂O₃ S/ F/ Cl/ Y₂O₃ Y₂O₃ Y₂O₃ La₂O₃ S/ F/ Cl/ La₂O₃La₂O₃ La₂O₃ CeO₂ S/ F/ Cl/ CeO₂ CeO₂ CeO₂ Ce₂O₃ S/ F/ Cl/ Ce₂O₃ Ce₂O₃Ce₂O₃ Pr₂O₃ S/ F/ Cl/ Pr₂O₃ Pr₂O₃ Pr₂O₃ Nd₂O₃ S/ F/ Cl/ Nd₂O₃ Nd₂O₃Nd₂O₃ Sm₂O₃ S/ F/ Cl/ Sm₂O₃ Sm₂O₃ Sm₂O₃ Eu₂O₃ S/ F/ Cl/ Eu₂O₃ Eu₂O₃Eu₂O₃ Gd₂O₃ S/ F/ Cl/ Gd₂O₃ Gd₂O₃ Gd₂O₃ Tb₂O₃ S/ F/ Cl/ Tb₂O₃ Tb₂O₃Tb₂O₃ TbO₂ S/ F/ Cl/ TbO₂ TbO₂ TbO₂ Tb₆O₁₁ S/ F/ Cl/ Tb₆O₁₁ Tb₆O₁₁Tb₆O₁₁ Dy₂O₃ S/ F/ Cl/ Dy₂O₃ Dy₂O₃ Dy₂O₃ Ho₂O₃ S/ F/ Cl/ Ho₂O₃ Ho₂O₃Ho₂O₃ Er₂O₃ S/ F/ Cl/ Er₂O₃ Er₂O₃ Er₂O₃ Tm₂O₃ S/ F/ Cl/ Tm₂O₃ Tm₂O₃Tm₂O₃ Yb₂O₃ S/ F/ Cl/ Yb₂O₃ Yb₂O₃ Yb₂O₃ Lu₂O₃ S/ F/ Cl/ Lu₂O₃ Lu₂O₃Lu₂O₃ Ac₂O₃ S/ F/ Cl/ Ac₂O₃ Ac₂O₃ Ac₂O₃ Th₂O₃ S/ F/ Cl/ Th₂O₃ Th₂O₃Th₂O₃ ThO₂ S/ F/ Cl/ ThO₂ ThO₂ ThO₂ Pa₂O₃ S/ F/ Cl/ Pa₂O₃ Pa₂O₃ Pa₂O₃PaO₂ S/ F/ Cl/ PaO₂ PaO₂ PaO₂ TiO₂ S/ F/ Cl/ TiO₂ TiO₂ TiO₂ TiO S/ F/Cl/ TiO TiO TiO Ti₂O₃ S/ F/ Cl/ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₃O S/ F/ Cl/ Ti₃OTi₃O Ti₃O Ti₂O S/ F/ Cl/ Ti₂O Ti₂O Ti₂O Ti₃O₅ S/ F/ Cl/ Ti₃O₅ Ti₃O₅Ti₃O₅ Ti₄O₇ S/ F/ Cl/ Ti₄O₇ Ti₄O₇ Ti₄O₇ ZrO₂ S/ F/ Cl/ ZrO₂ ZrO₂ ZrO₂HfO₂ S/ F/ Cl/ HfO₂ HfO₂ HfO₂ VO S/ F/ Cl/ VO VO VO V₂O₃ S/ F/ Cl/ V₂O₃V₂O₃ V₂O₃ VO₂ S/ F/ Cl/ VO₂ VO₂ VO₂ V₂O₅ S/ F/ Cl/ V₂O₅ V₂O₅ V₂O₅ V₃O₇S/ F/ Cl/ V₃O₇ V₃O₇ V₃O₇ V₄O₉ S/ F/ Cl/ V₄O₉ V₄O₉ V₄O₉ V₆O₁₃ S/ F/ Cl/V₆O₁₃ V₆O₁₃ V₆O₁₃ NbO S/ F/ Cl/ NbO NbO NbO NbO₂ S/ F/ Cl/ NbO₂ NbO₂NbO₂ Nb₂O₅ S/ F/ Cl/ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₈O₁₉ S/ F/ Cl/ Nb₈O₁₉ Nb₈O₁₉Nb₈O₁₉ Nb₁₆O₃₈ S/ F/ Cl/ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₂O₂₉ S/ F/ Cl/Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₄₇O₁₁₆ S/ F/ Cl/ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆Ta₂O₅ S/ F/ Cl/ Ta₂O₅ Ta₂O₅ Ta₂O₅ CrO S/ F/ Cl/ CrO CrO CrO Cr₂O₃ S/ F/Cl/ Cr₂O₃ Cr₂O₃ Cr₂O₃ CrO₂ S/ F/ Cl/ CrO₂ CrO₂ CrO₂ CrO₃ S/ F/ Cl/ CrO₃CrO₃ CrO₃ Cr₈O₂₁ S/ F/ Cl/ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ MoO₂ S/ F/ Cl/ MoO₂ MoO₂MoO₂ MoO₃ S/ F/ Cl/ MoO₃ MoO₃ MoO₃ W₂O₃ S/ F/ Cl/ W₂O₃ W₂O₃ W₂O₃ WoO₂ S/F/ Cl/ WoO₂ WoO₂ WoO₂ WoO₃ S/ F/ Cl/ WoO₃ WoO₃ WoO₃ MnO S/ F/ Cl/ MnOMnO MnO Mn/Mg/O S/ F/ Cl/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn₃O₄ S/ F/ Cl/ Mn₃O₄Mn₃O₄ Mn₃O₄ Mn₂O₃ S/ F/ Cl/ Mn₂O₃ Mn₂O₃ Mn₂O₃ MnO₂ S/ F/ Cl/ MnO₂ MnO₂MnO₂ Mn₂O₇ S/ F/ Cl/ Mn₂O₇ Mn₂O₇ Mn₂O₇ ReO₂ S/ F/ Cl/ ReO₂ ReO₂ ReO₂ReO₃ S/ F/ Cl/ ReO₃ ReO₃ ReO₃ Re₂O₇ S/ F/ Cl/ Re₂O₇ Re₂O₇ Re₂O₇Mg₃Mn₃—B₂O₁₀ S/ F/ Cl/ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀ Mg₃(BO₃)₂S/ F/ Cl/ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂ NaWO₄ S/ F/ Cl/ NaWO₄ NaWO₄NaWO₄ Mg₆MnO₈ S/ F/ Cl/ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ (Li,Mg)₆MnO₈ S/ F/ Cl/(Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ Mn₂O₄ S/ F/ Cl/ Mn₂O₄ Mn₂O₄ Mn₂O₄Na₄P₂O₇ S/ F/ Cl/ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Mo₂O₈ S/ F/ Cl/ Mo₂O₈ Mo₂O₈Mo₂O₈ Mn₃O₄/WO₄ S/ F/ Cl/ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Na₂WO₄ S/ F/ Cl/Na₂WO₄ Na₂WO₄ Na₂WO₄ Zr₂Mo₂O₈ S/ F/ Cl/ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈NaMnO₄/MgO S/ F/ Cl/ NaMnO₄/MgO NaMnO₄/MgO NaMnO₄/MgO Na₁₀Mn—W₅O₁₇ S/ F/Cl/ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ La₃NdO₆ S/ F/ Cl/ La₃NdO₆La₃NdO₆ La₃NdO₆ LaNd₃O₆ S/ F/ Cl/ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆La_(1,5)Nd_(2,5)O₆ S/ F/ Cl/ La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆La_(1,5)Nd_(2,5)O₆ La_(2,5)Nd_(1,5)O₆ S/ F/ Cl/ La_(2,5)Nd_(1,5)O₆La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆ La_(3,2)Nd_(0,8)O₆ S/ F/ Cl/La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆La_(3,5)Nd_(0,5)O₆ S/ F/ Cl/ La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆La_(3,5)Nd_(0,5)O₆ La_(3,8)Nd_(0,2)O₆ S/ F/ Cl/ La_(3,8)Nd_(0,2)O₆La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆ Y—La S/ F/ Cl/ Y—La Y—La Y—LaZr—La S/ F/ Cl/ Zr—La Zr—La Zr—La Pr—La S/ F/ Cl/ Pr—La Pr—La Pr—LaCe—La S/ F/ Cl/ Ce—La Ce—La Ce—La

TABLE 3 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS (DOP) Dop NW La Ce PrNd Li₂O La/ Ce/ Pr/ Nd/ Li₂O Li₂O Li₂O Li₂O Na₂O La/ Ce/ Pr/ Nd/ Na₂ONa₂O Na₂O Na₂O K₂O La/ Ce/ Pr/ Nd/ K₂O K₂O K₂O K₂O Rb₂O La/ Ce/ Pr/ Nd/Rb₂O Rb₂O Rb₂O Rb₂O Cs₂O La/ Ce/ Pr/ Nd/ Cs₂O Cs₂O Cs₂O Cs₂O BeO La/ Ce/Pr/ Nd/ BeO BeO BeO BeO MgO La/ Ce/ Pr/ Nd/ MgO MgO MgO MgO CaO La/ Ce/Pr/ Nd/ CaO CaO CaO CaO SrO La/ Ce/ Pr/ Nd/ SrO SrO SrO SrO BaO La/ Ce/Pr/ Nd/ BaO BaO BaO BaO Sc₂O₃ La/ Ce/ Pr/ Nd/ Sc₂O₃ Sc₂O₃ Sc₂O₃ Sc₂O₃Y₂O₃ La/ Ce/ Pr/ Nd/ Y₂O₃ Y₂O₃ Y₂O₃ Y₂O₃ La₂O₃ La/ Ce/ Pr/ Nd/ La₂O₃La₂O₃ La₂O₃ La₂O₃ CeO₂ La/ Ce/ Pr/ Nd/ CeO₂ CeO₂ CeO₂ CeO₂ Ce₂O₃ La/ Ce/Pr/ Nd/ Ce₂O₃ Ce₂O₃ Ce₂O₃ Ce₂O₃ Pr₂O₃ La/ Ce/ Pr/ Nd/ Pr₂O₃ Pr₂O₃ Pr₂O₃Pr₂O₃ Nd₂O₃ La/ Ce/ Pr/ Nd/ Nd₂O₃ Nd₂O₃ Nd₂O₃ Nd₂O₃ Sm₂O₃ La/ Ce/ Pr/Nd/ Sm₂O₃ Sm₂O₃ Sm₂O₃ Sm₂O₃ Eu₂O₃ La/ Ce/ Pr/ Nd/ Eu₂O₃ Eu₂O₃ Eu₂O₃Eu₂O₃ Gd₂O₃ La/ Ce/ Pr/ Nd/ Gd₂O₃ Gd₂O₃ Gd₂O₃ Gd₂O₃ Tb₂O₃ La/ Ce/ Pr/Nd/ Tb₂O₃ Tb₂O₃ Tb₂O₃ Tb₂O₃ TbO₂ La/ Ce/ Pr/ Nd/ TbO₂ TbO₂ TbO₂ TbO₂Tb₆O₁₁ La/ Ce/ Pr/ Nd/ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Dy₂O₃ La/ Ce/ Pr/ Nd/Dy₂O₃ Dy₂O₃ Dy₂O₃ Dy₂O₃ Ho₂O₃ La/ Ce/ Pr/ Nd/ Ho₂O₃ Ho₂O₃ Ho₂O₃ Ho₂O₃Er₂O₃ La/ Ce/ Pr/ Nd/ Er₂O₃ Er₂O₃ Er₂O₃ Er₂O₃ Tm₂O₃ La/ Ce/ Pr/ Nd/Tm₂O₃ Tm₂O₃ Tm₂O₃ Tm₂O₃ Yb₂O₃ La/ Ce/ Pr/ Nd/ Yb₂O₃ Yb₂O₃ Yb₂O₃ Yb₂O₃Lu₂O₃ La/ Ce/ Pr/ Nd/ Lu₂O₃ Lu₂O₃ Lu₂O₃ Lu₂O₃ Ac₂O₃ La/ Ce/ Pr/ Nd/Ac₂O₃ Ac₂O₃ Ac₂O₃ Ac₂O₃ Th₂O₃ La/ Ce/ Pr/ Nd/ Th₂O₃ Th₂O₃ Th₂O₃ Th₂O₃ThO₂ La/ Ce/ Pr/ Nd/ ThO₂ ThO₂ ThO₂ ThO₂ Pa₂O₃ La/ Ce/ Pr/ Nd/ Pa₂O₃Pa₂O₃ Pa₂O₃ Pa₂O₃ PaO₂ La/ Ce/ Pr/ Nd/ PaO₂ PaO₂ PaO₂ PaO₂ TiO₂ La/ Ce/Pr/ Nd/ TiO₂ TiO₂ TiO₂ TiO₂ TiO La/ Ce/ Pr/ Nd/ TiO TiO TiO TiO Ti₂O₃La/ Ce/ Pr/ Nd/ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₃O La/ Ce/ Pr/ Nd/ Ti₃O Ti₃OTi₃O Ti₃O Ti₂O La/ Ce/ Pr/ Nd/ Ti₂O Ti₂O Ti₂O Ti₂O Ti₃O₅ La/ Ce/ Pr/ Nd/Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₄O₇ La/ Ce/ Pr/ Nd/ Ti₄O₇ Ti₄O₇ Ti₄O₇ Ti₄O₇ZrO₂ La/ Ce/ Pr/ Nd/ ZrO₂ ZrO₂ ZrO₂ ZrO₂ HfO₂ La/ Ce/ Pr/ Nd/ HfO₂ HfO₂HfO₂ HfO₂ VO La/ Ce/ Pr/ Nd/ VO VO VO VO V₂O₃ La/ Ce/ Pr/ Nd/ V₂O₃ V₂O₃V₂O₃ V₂O₃ VO₂ La/ Ce/ Pr/ Nd/ VO₂ VO₂ VO₂ VO₂ V₂O₅ La/ Ce/ Pr/ Nd/ V₂O₅V₂O₅ V₂O₅ V₂O₅ V₃O₇ La/ Ce/ Pr/ Nd/ V₃O₇ V₃O₇ V₃O₇ V₃O₇ V₄O₉ La/ Ce/ Pr/Nd/ V₄O₉ V₄O₉ V₄O₉ V₄O₉ V₆O₁₃ La/ Ce/ Pr/ Nd/ V₆O₁₃ V₆O₁₃ V₆O₁₃ V₆O₁₃NbO La/ Ce/ Pr/ Nd/ NbO NbO NbO NbO NbO₂ La/ Ce/ Pr/ Nd/ NbO₂ NbO₂ NbO₂NbO₂ Nb₂O₅ La/ Ce/ Pr/ Nd/ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₈O₁₉ La/ Ce/ Pr/Nd/ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₁₆O₃₈ La/ Ce/ Pr/ Nd/ Nb₁₆O₃₈ Nb₁₆O₃₈Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₂O₂₉ La/ Ce/ Pr/ Nd/ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉Nb₄₇O₁₁₆ La/ Ce/ Pr/ Nd/ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Ta₂O₅ La/Ce/ Pr/ Nd/ Ta₂O₅ Ta₂O₅ Ta₂O₅ Ta₂O₅ CrO La/ Ce/ Pr/ Nd/ CrO CrO CrO CrOCr₂O₃ La/ Ce/ Pr/ Nd/ Cr₂O₃ Cr₂O₃ Cr₂O₃ Cr₂O₃ CrO₂ La/ Ce/ Pr/ Nd/ CrO₂CrO₂ CrO₂ CrO₂ CrO₃ La/ Ce/ Pr/ Nd/ CrO₃ CrO₃ CrO₃ CrO₃ Cr₈O₂₁ La/ Ce/Pr/ Nd/ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ MoO₂ La/ Ce/ Pr/ Nd/ MoO₂ MoO₂ MoO₂MoO₂ MoO₃ La/ Ce/ Pr/ Nd/ MoO₃ MoO₃ MoO₃ MoO₃ W₂O₃ La/ Ce/ Pr/ Nd/ W₂O₃W₂O₃ W₂O₃ W₂O₃ WoO₂ La/ Ce/ Pr/ Nd/ WoO₂ WoO₂ WoO₂ WoO₂ WoO₃ La/ Ce/ Pr/Nd/ WoO₃ WoO₃ WoO₃ WoO₃ MnO La/ Ce/ Pr/ Nd/ MnO MnO MnO MnO Mn/Mg/O La/Ce/ Pr/ Nd/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn₃O₄ La/ Ce/ Pr/ Nd/ Mn₃O₄Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₂O₃ La/ Ce/ Pr/ Nd/ Mn₂O₃ Mn₂O₃ Mn₂O₃ Mn₂O₃ MnO₂ La/Ce/ Pr/ Nd/ MnO₂ MnO₂ MnO₂ MnO₂ Mn₂O₇ La/ Ce/ Pr/ Nd/ Mn₂O₇ Mn₂O₇ Mn₂O₇Mn₂O₇ ReO₂ La/ Ce/ Pr/ Nd/ ReO₂ ReO₂ ReO₂ ReO₂ ReO₃ La/ Ce/ Pr/ Nd/ ReO₃ReO₃ ReO₃ ReO₃ Re₂O₇ La/ Ce/ Pr/ Nd/ Re₂O₇ Re₂O₇ Re₂O₇ Re₂O₇Mg₃Mn₃—B₂O₁₀ La/ Ce/ Pr/ Nd/ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀Mg₃Mn₃—B₂O₁₀ Mg₃(BO₃)₂ La/ Ce/ Pr/ Nd/ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂Mg₃(BO₃)₂ NaWO₄ La/ Ce/ Pr/ Nd/ NaWO₄ NaWO₄ NaWO₄ NaWO₄ Mg₆MnO₈ La/ Ce/Pr/ Nd/ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ (Li,Mg)₆MnO₈ La/ Ce/ Pr/ Nd/(Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ Mn₂O₄ La/ Ce/ Pr/Nd/ Mn₂O₄ Mn₂O₄ Mn₂O₄ Mn₂O₄ Na₄P₂O₇ La/ Ce/ Pr/ Nd/ Na₄P₂O₇ Na₄P₂O₇Na₄P₂O₇ Na₄P₂O₇ Mo₂O₈ La/ Ce/ Pr/ Nd/ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mn₃O₄/WO₄La/ Ce/ Pr/ Nd/ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Na₂WO₄ La/ Ce/Pr/ Nd/ Na₂WO₄ Na₂WO₄ Na₂WO₄ Na₂WO₄ Zr₂Mo₂O₈ La/ Ce/ Pr/ Nd/ Zr₂Mo₂O₈Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ NaMnO₄—/ La/ Ce/ Pr/ Nd/ MgO NaMnO₄—/NaMnO₄—/ NaMnO₄—/ NaMnO₄—/ MgO MgO MgO MgO Na₁₀Mn—W₅O₁₇ La/ Ce/ Pr/ Nd/Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ La₃NdO₆ La/ Ce/ Pr/Nd/ La₃NdO₆ La₃NdO₆ La₃NdO₆ La₃NdO₆ LaNd₃O₆ La/ Ce/ Pr/ Nd/ LaNd₃O₆LaNd₃O₆ LaNd₃O₆ LaNd₃O₆ La_(1,5)Nd_(2,5)O₆ La/ Ce/ Pr/ Nd/La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆La_(1,5)Nd_(2,5)O₆ La_(2,5)Nd_(1,5)O₆ La/ Ce/ Pr/ Nd/ La_(2,5)Nd_(1,5)O₆La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆La_(3,2)Nd_(0,8)O₆ La/ Ce/ Pr/ Nd/ La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆ La_(3,5)Nd_(0,5)O₆ La/ Ce/ Pr/ Nd/La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆La_(3,5)Nd_(0,5)O₆ La_(3,8)Nd_(0,2)O₆ La/ Ce/ Pr/ Nd/ La_(3,8)Nd_(0,2)O₆La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆ Y—La La/ Ce/Pr/ Nd/ Y—La Y—La Y—La Y—La Zr—La La/ Ce/ Pr/ Nd/ Zr—La Zr—La Zr—LaZr—La Pr—La La/ Ce/ Pr/ Nd/ Pr—La Pr—La Pr—La Pr—La Ce—La La/ Ce/ Pr/Nd/ Ce—La Ce—La Ce—La Ce—La Dop NW Pm Sm Eu Gd Li₂O Pm/ Sm/ Eu/ Gd/ Li₂OLi₂O Li₂O Li₂O Na₂O Pm/ Sm/ Eu/ Gd/ Na₂O Na₂O Na₂O Na₂O K₂O Pm/ Sm/ Eu/Gd/ K₂O K₂O K₂O K₂O Rb₂O Pm/ Sm/ Eu/ Gd/ Rb₂O Rb₂O Rb₂O Rb₂O Cs₂O Pm/Sm/ Eu/ Gd/ Cs₂O Cs₂O Cs₂O Cs₂O BeO Pm/ Sm/ Eu/ Gd/ BeO BeO BeO BeO MgOPm/ Sm/ Eu/ Gd/ MgO MgO MgO MgO CaO Pm/ Sm/ Eu/ Gd/ CaO CaO CaO CaO SrOPm/ Sm/ Eu/ Gd/ SrO SrO SrO SrO BaO Pm/ Sm/ Eu/ Gd/ BaO BaO BaO BaOSc₂O₃ Pm/ Sm/ Eu/ Gd/ Sc₂O₃ Sc₂O₃ Sc₂O₃ Sc₂O₃ Y₂O₃ Pm/ Sm/ Eu/ Gd/ Y₂O₃Y₂O₃ Y₂O₃ Y₂O₃ La₂O₃ Pm/ Sm/ Eu/ Gd/ La₂O₃ La₂O₃ La₂O₃ La₂O₃ CeO₂ Pm/Sm/ Eu/ Gd/ CeO₂ CeO₂ CeO₂ CeO₂ Ce₂O₃ Pm/ Sm/ Eu/ Gd/ Ce₂O₃ Ce₂O₃ Ce₂O₃Ce₂O₃ Pr₂O₃ Pm/ Sm/ Eu/ Gd/ Pr₂O₃ Pr₂O₃ Pr₂O₃ Pr₂O₃ Nd₂O₃ Pm/ Sm/ Eu/Gd/ Nd₂O₃ Nd₂O₃ Nd₂O₃ Nd₂O₃ Sm₂O₃ Pm/ Sm/ Eu/ Gd/ Sm₂O₃ Sm₂O₃ Sm₂O₃Sm₂O₃ Eu₂O₃ Pm/ Sm/ Eu/ Gd/ Eu₂O₃ Eu₂O₃ Eu₂O₃ Eu₂O₃ Gd₂O₃ Pm/ Sm/ Eu/Gd/ Gd₂O₃ Gd₂O₃ Gd₂O₃ Gd₂O₃ Tb₂O₃ Pm/ Sm/ Eu/ Gd/ Tb₂O₃ Tb₂O₃ Tb₂O₃Tb₂O₃ TbO₂ Pm/ Sm/ Eu/ Gd/ TbO₂ TbO₂ TbO₂ TbO₂ Tb₆O₁₁ Pm/ Sm/ Eu/ Gd/Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Dy₂O₃ Pm/ Sm/ Eu/ Gd/ Dy₂O₃ Dy₂O₃ Dy₂O₃Dy₂O₃ Ho₂O₃ Pm/ Sm/ Eu/ Gd/ Ho₂O₃ Ho₂O₃ Ho₂O₃ Ho₂O₃ Er₂O₃ Pm/ Sm/ Eu/Gd/ Er₂O₃ Er₂O₃ Er₂O₃ Er₂O₃ Tm₂O₃ Pm/ Sm/ Eu/ Gd/ Tm₂O₃ Tm₂O₃ Tm₂O₃Tm₂O₃ Yb₂O₃ Pm/ Sm/ Eu/ Gd/ Yb₂O₃ Yb₂O₃ Yb₂O₃ Yb₂O₃ Lu₂O₃ Pm/ Sm/ Eu/Gd/ Lu₂O₃ Lu₂O₃ Lu₂O₃ Lu₂O₃ Ac₂O₃ Pm/ Sm/ Eu/ Gd/ Ac₂O₃ Ac₂O₃ Ac₂O₃Ac₂O₃ Th₂O₃ Pm/ Sm/ Eu/ Gd/ Th₂O₃ Th₂O₃ Th₂O₃ Th₂O₃ ThO₂ Pm/ Sm/ Eu/ Gd/ThO₂ ThO₂ ThO₂ ThO₂ Pa₂O₃ Pm/ Sm/ Eu/ Gd/ Pa₂O₃ Pa₂O₃ Pa₂O₃ Pa₂O₃ PaO₂Pm/ Sm/ Eu/ Gd/ PaO₂ PaO₂ PaO₂ PaO₂ TiO₂ Pm/ Sm/ Eu/ Gd/ TiO₂ TiO₂ TiO₂TiO₂ TiO Pm/ Sm/ Eu/ Gd/ TiO TiO TiO TiO Ti₂O₃ Pm/ Sm/ Eu/ Gd/ Ti₂O₃Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₃O Pm/ Sm/ Eu/ Gd/ Ti₃O Ti₃O Ti₃O Ti₃O Ti₂O Pm/ Sm/Eu/ Gd/ Ti₂O Ti₂O Ti₂O Ti₂O Ti₃O₅ Pm/ Sm/ Eu/ Gd/ Ti₃O₅ Ti₃O₅ Ti₃O₅Ti₃O₅ Ti₄O₇ Pm/ Sm/ Eu/ Gd/ Ti₄O₇ Ti₄O₇ Ti₄O₇ Ti₄O₇ ZrO₂ Pm/ Sm/ Eu/ Gd/ZrO₂ ZrO₂ ZrO₂ ZrO₂ HfO₂ Pm/ Sm/ Eu/ Gd/ HfO₂ HfO₂ HfO₂ HfO₂ VO Pm/ Sm/Eu/ Gd/ VO VO VO VO V₂O₃ Pm/ Sm/ Eu/ Gd/ V₂O₃ V₂O₃ V₂O₃ V₂O₃ VO₂ Pm/ Sm/Eu/ Gd/ VO₂ VO₂ VO₂ VO₂ V₂O₅ Pm/ Sm/ Eu/ Gd/ V₂O₅ V₂O₅ V₂O₅ V₂O₅ V₃O₇Pm/ Sm/ Eu/ Gd/ V₃O₇ V₃O₇ V₃O₇ V₃O₇ V₄O₉ Pm/ Sm/ Eu/ Gd/ V₄O₉ V₄O₉ V₄O₉V₄O₉ V₆O₁₃ Pm/ Sm/ Eu/ Gd/ V₆O₁₃ V₆O₁₃ V₆O₁₃ V₆O₁₃ NbO Pm/ Sm/ Eu/ Gd/NbO NbO NbO NbO NbO₂ Pm/ Sm/ Eu/ Gd/ NbO₂ NbO₂ NbO₂ NbO₂ Nb₂O₅ Pm/ Sm/Eu/ Gd/ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₈O₁₉ Pm/ Sm/ Eu/ Gd/ Nb₈O₁₉ Nb₈O₁₉Nb₈O₁₉ Nb₈O₁₉ Nb₁₆O₃₈ Pm/ Sm/ Eu/ Gd/ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈Nb₁₂O₂₉ Pm/ Sm/ Eu/ Gd/ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₄₇O₁₁₆ Pm/ Sm/Eu/ Gd/ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Ta₂O₅ Pm/ Sm/ Eu/ Gd/ Ta₂O₅Ta₂O₅ Ta₂O₅ Ta₂O₅ CrO Pm/ Sm/ Eu/ Gd/ CrO CrO CrO CrO Cr₂O₃ Pm/ Sm/ Eu/Gd/ Cr₂O₃ Cr₂O₃ Cr₂O₃ Cr₂O₃ CrO₂ Pm/ Sm/ Eu/ Gd/ CrO₂ CrO₂ CrO₂ CrO₂CrO₃ Pm/ Sm/ Eu/ Gd/ CrO₃ CrO₃ CrO₃ CrO₃ Cr₈O₂₁ Pm/ Sm/ Eu/ Gd/ Cr₈O₂₁Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ MoO₂ Pm/ Sm/ Eu/ Gd/ MoO₂ MoO₂ MoO₂ MoO₂ MoO₃ Pm/Sm/ Eu/ Gd/ MoO₃ MoO₃ MoO₃ MoO₃ W₂O₃ Pm/ Sm/ Eu/ Gd/ W₂O₃ W₂O₃ W₂O₃ W₂O₃WoO₂ Pm/ Sm/ Eu/ Gd/ WoO₂ WoO₂ WoO₂ WoO₂ WoO₃ Pm/ Sm/ Eu/ Gd/ WoO₃ WoO₃WoO₃ WoO₃ MnO Pm/ Sm/ Eu/ Gd/ MnO MnO MnO MnO Mn/Mg/O Pm/ Sm/ Eu/ Gd/Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn₃O₄ Pm/ Sm/ Eu/ Gd/ Mn₃O₄ Mn₃O₄ Mn₃O₄Mn₃O₄ Mn₂O₃ Pm/ Sm/ Eu/ Gd/ Mn₂O₃ Mn₂O₃ Mn₂O₃ Mn₂O₃ MnO₂ Pm/ Sm/ Eu/ Gd/MnO₂ MnO₂ MnO₂ MnO₂ Mn₂O₇ Pm/ Sm/ Eu/ Gd/ Mn₂O₇ Mn₂O₇ Mn₂O₇ Mn₂O₇ ReO₂Pm/ Sm/ Eu/ Gd/ ReO₂ ReO₂ ReO₂ ReO₂ ReO₃ Pm/ Sm/ Eu/ Gd/ ReO₃ ReO₃ ReO₃ReO₃ Re₂O₇ Pm/ Sm/ Eu/ Gd/ Re₂O₇ Re₂O₇ Re₂O₇ Re₂O₇ Mg₃Mn₃—B₂O₁₀ Pm/ Sm/Eu/ Gd/ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀ Mg₃(BO₃)₂Pm/ Sm/ Eu/ Gd/ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂ NaWO₄ Pm/ Sm/Eu/ Gd/ NaWO₄ NaWO₄ NaWO₄ NaWO₄ Mg₆MnO₈ Pm/ Sm/ Eu/ Gd/ Mg₆MnO₈ Mg₆MnO₈Mg₆MnO₈ Mg₆MnO₈ (Li,Mg)₆MnO₈ Pm/ Sm/ Eu/ Gd/ (Li,Mg)₆MnO8 (Li,Mg)₆MnO₈(Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ Mn₂O₄ Pm/ Sm/ Eu/ Gd/ Mn₂O₄ Mn₂O₄ Mn₂O₄ Mn₂O₄Na₄P₂O₇ Pm/ Sm/ Eu/ Gd/ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Mo₂O₈ Pm/ Sm/Eu/ Gd/ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mn₃O₄/WO₄ Pm/ Sm/ Eu/ Gd/ Mn₃O₄/WO₄Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Na₂WO₄ Pm/ Sm/ Eu/ Gd/ Na₂WO₄ Na₂WO₄Na₂WO₄ Na₂WO₄ Zr₂Mo₂O₈ Pm/ Sm/ Eu/ Gd/ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈Zr₂Mo₂O₈ NaMnO₄—/ Pm/ Sm/ Eu/ Gd/ MgO NaMnO₄—/ NaMnO₄—/ NaMnO₄—/NaMnO₄—/ MgO MgO MgO MgO Na₁₀Mn—W₅O₁₇ Pm/ Sm/ Eu/ Gd/ Na₁₀Mn—W₅O₁₇Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ La₃NdO₆ Pm/ Sm/ Eu/ Gd/ La₃NdO₆La₃NdO₆ La₃NdO₆ La₃NdO₆ LaNd₃O₆ Pm/ Sm/ Eu/ Gd/ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆LaNd₃O₆ La_(1,5)Nd_(2,5)O₆ Pm/ Sm/ Eu/ Gd/ La_(1,5)Nd_(2,5)O₆La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆La_(2,5)Nd_(1,5)O₆ Pm/ Sm/ Eu/ Gd/ La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆ La_(3,2)Nd_(0,8)O₆ Pm/ Sm/ Eu/ Gd/La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆La_(3,2)Nd_(0,8)O₆ La_(3,5)Nd_(0,5)O₆ Pm/ Sm/ Eu/ Gd/ La_(3,5)Nd_(0,5)O₆La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆La_(3,8)Nd_(0,2)O₆ Pm/ Sm/ Eu/ Gd/ La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆ Y—La Pm/ Sm/ Eu/ Gd/ Y—La Y—LaY—La Y—La Zr—La Pm/ Sm/ Eu/ Gd/ Zr—La Zr—La Zr—La Zr—La Pr—La Pm/ Sm/Eu/ Gd/ Pr—La Pr—La Pr—La Pr—La Ce—La Pm/ Sm/ Eu/ Gd/ Ce—La Ce—La Ce—LaCe—La

TABLE 4 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS (DOP) Dop NW Tb Dy HoEr Li₂O Tb/ Dy/ Ho/ Er/ Li₂O Li₂O Li₂O Li₂O Na₂O Tb/ Dy/ Ho/ Er/ Na₂ONa₂O Na₂O Na₂O K₂O Tb/ Dy/ Ho/ Er/ K₂O K₂O K₂O K₂O Rb₂O Tb/ Dy/ Ho/ Er/Rb₂O Rb₂O Rb₂O Rb₂O Cs₂O Tb/ Dy/ Ho/ Er/ Cs₂O Cs₂O Cs₂O Cs₂O BeO Tb/ Dy/Ho/ Er/ BeO BeO BeO BeO MgO Tb/ Dy/ Ho/ Er/ MgO MgO MgO MgO CaO Tb/ Dy/Ho/ Er/ CaO CaO CaO CaO SrO Tb/ Dy/ Ho/ Er/ SrO SrO SrO SrO BaO Tb/ Dy/Ho/ Er/ BaO BaO BaO BaO Sc₂O₃ Tb/ Dy/ Ho/ Er/ Sc₂O₃ Sc₂O₃ Sc₂O₃ Sc₂O₃Y₂O₃ Tb/ Dy/ Ho/ Er/ Y₂O₃ Y₂O₃ Y₂O₃ Y₂O₃ La₂O₃ Tb/ Dy/ Ho/ Er/ La₂O₃La₂O₃ La₂O₃ La₂O₃ CeO₂ Tb/ Dy/ Ho/ Er/ CeO₂ CeO₂ CeO₂ CeO₂ Ce₂O₃ Tb/ Dy/Ho/ Er/ Ce₂O₃ Ce₂O₃ Ce₂O₃ Ce₂O₃ Pr₂O₃ Tb/ Dy/ Ho/ Er/ Pr₂O₃ Pr₂O₃ Pr₂O₃Pr₂O₃ Nd₂O₃ Tb/ Dy/ Ho/ Er/ Nd₂O₃ Nd₂O₃ Nd₂O₃ Nd₂O₃ Sm₂O₃ Tb/ Dy/ Ho/Er/ Sm₂O₃ Sm₂O₃ Sm₂O₃ Sm₂O₃ Eu₂O₃ Tb/ Dy/ Ho/ Er/ Eu₂O₃ Eu₂O₃ Eu₂O₃Eu₂O₃ Gd₂O₃ Tb/ Dy/ Ho/ Er/ Gd₂O₃ Gd₂O₃ Gd₂O₃ Gd₂O₃ Tb₂O₃ Tb/ Dy/ Ho/Er/ Tb₂O₃ Tb₂O₃ Tb₂O₃ Tb₂O₃ TbO₂ Tb/ Dy/ Ho/ Er/ TbO₂ TbO₂ TbO₂ TbO₂Tb₆O₁₁ Tb/ Dy/ Ho/ Er/ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Dy₂O₃ Tb/ Dy/ Ho/ Er/Dy₂O₃ Dy₂O₃ Dy₂O₃ Dy₂O₃ Ho₂O₃ Tb/ Dy/ Ho/ Er/ Ho₂O₃ Ho₂O₃ Ho₂O₃ Ho₂O₃Er₂O₃ Tb/ Dy/ Ho/ Er/ Er₂O₃ Er₂O₃ Er₂O₃ Er₂O₃ Tm₂O₃ Tb/ Dy/ Ho/ Er/Tm₂O₃ Tm₂O₃ Tm₂O₃ Tm₂O₃ Yb₂O₃ Tb/ Dy/ Ho/ Er/ Yb₂O₃ Yb₂O₃ Yb₂O₃ Yb₂O₃Lu₂O₃ Tb/ Dy/ Ho/ Er/ Lu₂O₃ Lu₂O₃ Lu₂O₃ Lu₂O₃ Ac₂O₃ Tb/ Dy/ Ho/ Er/Ac₂O₃ Ac₂O₃ Ac₂O₃ Ac₂O₃ Th₂O₃ Tb/ Dy/ Ho/ Er/ Th₂O₃ Th₂O₃ Th₂O₃ Th₂O₃ThO₂ Tb/ Dy/ Ho/ Er/ ThO₂ ThO₂ ThO₂ ThO₂ Pa₂O₃ Tb/ Dy/ Ho/ Er/ Pa₂O₃Pa₂O₃ Pa₂O₃ Pa₂O₃ PaO₂ Tb/ Dy/ Ho/ Er/ PaO₂ PaO₂ PaO₂ PaO₂ TiO₂ Tb/ Dy/Ho/ Er/ TiO₂ TiO₂ TiO₂ TiO₂ TiO Tb/ Dy/ Ho/ Er/ TiO TiO TiO TiO Ti₂O₃Tb/ Dy/ Ho/ Er/ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₃O Tb/ Dy/ Ho/ Er/ Ti₃O Ti₃OTi₃O Ti₃O Ti₂O Tb/ Dy/ Ho/ Er/ Ti₂O Ti₂O Ti₂O Ti₂O Ti₃O₅ Tb/ Dy/ Ho/ Er/Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₄O₇ Tb/ Dy/ Ho/ Er/ Ti₄O₇ Ti₄O₇ Ti₄O₇ Ti₄O₇ZrO₂ Tb/ Dy/ Ho/ Er/ ZrO₂ ZrO₂ ZrO₂ ZrO₂ HfO₂ Tb/ Dy/ Ho/ Er/ HfO₂ HfO₂HfO₂ HfO₂ VO Tb/ Dy/ Ho/ Er/ VO VO VO VO V₂O₃ Tb/ Dy/ Ho/ Er/ V₂O₃ V₂O₃V₂O₃ V₂O₃ VO₂ Tb/ Dy/ Ho/ Er/ VO₂ VO₂ VO₂ VO₂ V₂O₅ Tb/ Dy/ Ho/ Er/ V₂O₅V₂O₅ V₂O₅ V₂O₅ V₃O₇ Tb/ Dy/ Ho/ Er/ V₃O₇ V₃O₇ V₃O₇ V₃O₇ V₄O₉ Tb/ Dy/ Ho/Er/ V₄O₉ V₄O₉ V₄O₉ V₄O₉ V₆O₁₃ Tb/ Dy/ Ho/ Er/ V₆O₁₃ V₆O₁₃ V₆O₁₃ V₆O₁₃NbO Tb/ Dy/ Ho/ Er/ NbO NbO NbO NbO NbO₂ Tb/ Dy/ Ho/ Er/ NbO₂ NbO₂ NbO₂NbO₂ Nb₂O₅ Tb/ Dy/ Ho/ Er/ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₈O₁₉ Tb/ Dy/ Ho/Er/ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₁₆O₃₈ Tb/ Dy/ Ho/ Er/ Nb₁₆O₃₈ Nb₁₆O₃₈Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₂O₂₉ Tb/ Dy/ Ho/ Er/ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉Nb₄₇O₁₁₆ Tb/ Dy/ Ho/ Er/ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Ta₂O₅ Tb/Dy/ Ho/ Er/ Ta₂O₅ Ta₂O₅ Ta₂O₅ Ta₂O₅ CrO Tb/ Dy/ Ho/ Er/ CrO CrO CrO CrOCr₂O₃ Tb/ Dy/ Ho/ Er/ Cr₂O₃ Cr₂O₃ Cr₂O₃ Cr₂O₃ CrO₂ Tb/ Dy/ Ho/ Er/ CrO₂CrO₂ CrO₂ CrO₂ CrO₃ Tb/ Dy/ Ho/ Er/ CrO₃ CrO₃ CrO₃ CrO₃ Cr₈O₂₁ Tb/ Dy/Ho/ Er/ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ MoO₂ Tb/ Dy/ Ho/ Er/ MoO₂ MoO₂ MoO₂MoO₂ MoO₃ Tb/ Dy/ Ho/ Er/ MoO₃ MoO₃ MoO₃ MoO₃ W₂O₃ Tb/ Dy/ Ho/ Er/ W₂O₃W₂O₃ W₂O₃ W₂O₃ WoO₂ Tb/ Dy/ Ho/ Er/ WoO₂ WoO₂ WoO₂ WoO₂ WoO₃ Tb/ Dy/ Ho/Er/ WoO₃ WoO₃ WoO₃ WoO₃ MnO Tb/ Dy/ Ho/ Er/ MnO MnO MnO MnO Mn/Mg/O Tb/Dy/ Ho/ Er/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn₃O₄ Tb/ Dy/ Ho/ Er/ Mn₃O₄Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₂O₃ Tb/ Dy/ Ho/ Er/ Mn₂O₃ Mn₂O₃ Mn₂O₃ Mn₂O₃ MnO₂ Tb/Dy/ Ho/ Er/ MnO₂ MnO₂ MnO₂ MnO₂ Mn₂O₇ Tb/ Dy/ Ho/ Er/ Mn₂O₇ Mn₂O₇ Mn₂O₇Mn₂O₇ ReO₂ Tb/ Dy/ Ho/ Er/ ReO₂ ReO₂ ReO₂ ReO₂ ReO₃ Tb/ Dy/ Ho/ Er/ ReO₃ReO₃ ReO₃ ReO₃ Re₂O₇ Tb/ Dy/ Ho/ Er/ Re₂O₇ Re₂O₇ Re₂O₇ Re₂O₇Mg₃Mn₃—B₂O₁₀ Tb/ Dy/ Ho/ Er/ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀Mg₃Mn₃—B₂O₁₀ Mg₃(BO₃)₂ Tb/ Dy/ Ho/ Er/ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂Mg₃(BO₃)₂ NaWO₄ Tb/ Dy/ Ho/ Er/ NaWO₄ NaWO₄ NaWO₄ NaWO₄ Mg₆MnO₈ Tb/ Dy/Ho/ Er/ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mn₂O₄ Tb/ Dy/ Ho/ Er/ Mn₂O₄Mn₂O₄ Mn₂O₄ Mn₂O₄ (Li,Mg)₆MnO₈ Tb/ Dy/ Ho/ Er/ (Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈(Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ Na₄P₂O₇ Tb/ Dy/ Ho/ Er/ Na₄P₂O₇ Na₄P₂O₇Na₄P₂O₇ Na₄P₂O₇ Mo₂O₈ Tb/ Dy/ Ho/ Er/ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mn₃O₄/WO₄Tb/ Dy/ Ho/ Er/ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Na₂WO₄ Tb/ Dy/Ho/ Er/ Na₂WO₄ Na₂WO₄ Na₂WO₄ Na₂WO₄ Zr₂Mo₂O₈ Tb/ Dy/ Ho/ Er/ Zr₂Mo₂O₈Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ NaMnO₄—/ Tb/ Dy/ Ho/ Er/ MgO NaMnO₄—/NaMnO₄—/ NaMnO₄—/ NaMnO₄—/ MgO MgO MgO MgO Na₁₀Mn—W₅O₁₇ Tb/ Dy/ Ho/ Er/Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ La₃NdO₆ Tb/ Dy/ Ho/Er/ La₃NdO₆ La₃NdO₆ La₃NdO₆ La₃NdO₆ LaNd₃O₆ Tb/ Dy/ Ho/ Er/ LaNd₃O₆LaNd₃O₆ LaNd₃O₆ LaNd₃O₆ La_(1,5)Nd_(2,5)O₆ Tb/ Dy/ Ho/ Er/La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆La_(1,5)Nd_(2,5)O₆ La_(2,5)Nd_(1,5)O₆ Tb/ Dy/ Ho/ Er/ La_(2,5)Nd_(1,5)O₆La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆La_(3,2)Nd_(0,8)O₆ Tb/ Dy/ Ho/ Er/ La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆ La_(3,5)Nd_(0,5)O₆ Tb/ Dy/ Ho/ Er/La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆La_(3,5)Nd_(0,5)O₆ La_(3,8)Nd_(0,2)O₆ Tb/ Dy/ Ho/ Er/ La_(3,8)Nd_(0,2)O₆La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆ Y—La Tb/ Dy/Ho/ Er/ Y—La Y—La Y—La Y—La Zr—La Tb/ Dy/ Ho/ Er/ Zr—La Zr—La Zr—LaZr—La Pr—La Tb/ Dy/ Ho/ Er/ Pr—La Pr—La Pr—La Pr—La Ce—La Tb/ Dy/ Ho/Er/ Ce—La Ce—La Ce—La Ce—La Dop NW Tm Yb Lu In Li₂O Tm/ Yb/ Lu/ In/ Li₂OLi₂O Li₂O Li₂O Na₂O Tm/ Yb/ Lu/ In/ Na₂O Na₂O Na₂O Na₂O K₂O Tm/ Yb/ Lu/In/ K₂O K₂O K₂O K₂O Rb₂O Tm/ Yb/ Lu/ In/ Rb₂O Rb₂O Rb₂O Rb₂O Cs₂O Tm/Yb/ Lu/ In/ Cs₂O Cs₂O Cs₂O Cs₂O BeO Tm/ Yb/ Lu/ In/ BeO BeO BeO BeO MgOTm/ Yb/ Lu/ In/ MgO MgO MgO MgO CaO Tm/ Yb/ Lu/ In/ CaO CaO CaO CaO SrOTm/ Yb/ Lu/ In/ SrO SrO SrO SrO BaO Tm/ Yb/ Lu/ In/ BaO BaO BaO BaOSc₂O₃ Tm/ Yb/ Lu/ In/ Sc₂O₃ Sc₂O₃ Sc₂O₃ Sc₂O₃ Y₂O₃ Tm/ Yb/ Lu/ In/ Y₂O₃Y₂O₃ Y₂O₃ Y₂O₃ La₂O₃ Tm/ Yb/ Lu/ In/ La₂O₃ La₂O₃ La₂O₃ La₂O₃ CeO₂ Tm/Yb/ Lu/ In/ CeO₂ CeO₂ CeO₂ CeO₂ Ce₂O₃ Tm/ Yb/ Lu/ In/ Ce₂O₃ Ce₂O₃ Ce₂O₃Ce₂O₃ Pr₂O₃ Tm/ Yb/ Lu/ In/ Pr₂O₃ Pr₂O₃ Pr₂O₃ Pr₂O₃ Nd₂O₃ Tm/ Yb/ Lu/In/ Nd₂O₃ Nd₂O₃ Nd₂O₃ Nd₂O₃ Sm₂O₃ Tm/ Yb/ Lu/ In/ Sm₂O₃ Sm₂O₃ Sm₂O₃Sm₂O₃ Eu₂O₃ Tm/ Yb/ Lu/ In/ Eu₂O₃ Eu₂O₃ Eu₂O₃ Eu₂O₃ Gd₂O₃ Tm/ Yb/ Lu/In/ Gd₂O₃ Gd₂O₃ Gd₂O₃ Gd₂O₃ Tb₂O₃ Tm/ Yb/ Lu/ In/ Tb₂O₃ Tb₂O₃ Tb₂O₃Tb₂O₃ TbO₂ Tm/ Yb/ Lu/ In/ TbO₂ TbO₂ TbO₂ TbO₂ Tb₆O₁₁ Tm/ Yb/ Lu/ In/Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Dy₂O₃ Tm/ Yb/ Lu/ In/ Dy₂O₃ Dy₂O₃ Dy₂O₃Dy₂O₃ Ho₂O₃ Tm/ Yb/ Lu/ In/ Ho₂O₃ Ho₂O₃ Ho₂O₃ Ho₂O₃ Er₂O₃ Tm/ Yb/ Lu/In/ Er₂O₃ Er₂O₃ Er₂O₃ Er₂O₃ Tm₂O₃ Tm/ Yb/ Lu/ In/ Tm₂O₃ Tm₂O₃ Tm₂O₃Tm₂O₃ Yb₂O₃ Tm/ Yb/ Lu/ In/ Yb₂O₃ Yb₂O₃ Yb₂O₃ Yb₂O₃ Lu₂O₃ Tm/ Yb/ Lu/In/ Lu₂O₃ Lu₂O₃ Lu₂O₃ Lu₂O₃ Ac₂O₃ Tm/ Yb/ Lu/ In/ Ac₂O₃ Ac₂O₃ Ac₂O₃Ac₂O₃ Th₂O₃ Tm/ Yb/ Lu/ In/ Th₂O₃ Th₂O₃ Th₂O₃ Th₂O₃ ThO₂ Tm/ Yb/ Lu/ In/ThO₂ ThO₂ ThO₂ ThO₂ Pa₂O₃ Tm/ Yb/ Lu/ In/ Pa₂O₃ Pa₂O₃ Pa₂O₃ Pa₂O₃ PaO₂Tm/ Yb/ Lu/ In/ PaO₂ PaO₂ PaO₂ PaO₂ TiO₂ Tm/ Yb/ Lu/ In/ TiO₂ TiO₂ TiO₂TiO₂ TiO Tm/ Yb/ Lu/ In/ TiO TiO TiO TiO Ti₂O₃ Tm/ Yb/ Lu/ In/ Ti₂O₃Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₃O Tm/ Yb/ Lu/ In/ Ti₃O Ti₃O Ti₃O Ti₃O Ti₂O Tm/ Yb/Lu/ In/ Ti₂O Ti₂O Ti₂O Ti₂O Ti₃O₅ Tm/ Yb/ Lu/ In/ Ti₃O₅ Ti₃O₅ Ti₃O₅Ti₃O₅ Ti₄O₇ Tm/ Yb/ Lu/ In/ Ti₄O₇ Ti₄O₇ Ti₄O₇ Ti₄O₇ ZrO₂ Tm/ Yb/ Lu/ In/ZrO₂ ZrO₂ ZrO₂ ZrO₂ HfO₂ Tm/ Yb/ Lu/ In/ HfO₂ HfO₂ HfO₂ HfO₂ VO Tm/ Yb/Lu/ In/ VO VO VO VO V₂O₃ Tm/ Yb/ Lu/ In/ V₂O₃ V₂O₃ V₂O₃ V₂O₃ VO₂ Tm/ Yb/Lu/ In/ VO₂ VO₂ VO₂ VO₂ V₂O₅ Tm/ Yb/ Lu/ In/ V₂O₅ V₂O₅ V₂O₅ V₂O₅ V₃O₇Tm/ Yb/ Lu/ In/ V₃O₇ V₃O₇ V₃O₇ V₃O₇ V₄O₉ Tm/ Yb/ Lu/ In/ V₄O₉ V₄O₉ V₄O₉V₄O₉ V₆O₁₃ Tm/ Yb/ Lu/ In/ V₆O₁₃ V₆O₁₃ V₆O₁₃ V₆O₁₃ NbO Tm/ Yb/ Lu/ In/NbO NbO NbO NbO NbO₂ Tm/ Yb/ Lu/ In/ NbO₂ NbO₂ NbO₂ NbO₂ Nb₂O₅ Tm/ Yb/Lu/ In/ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₈O₁₉ Tm/ Yb/ Lu/ In/ Nb₈O₁₉ Nb₈O₁₉Nb₈O₁₉ Nb₈O₁₉ Nb₁₆O₃₈ Tm/ Yb/ Lu/ In/ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈Nb₁₂O₂₉ Tm/ Yb/ Lu/ In/ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₄₇O₁₁₆ Tm/ Yb/Lu/ In/ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Ta₂O₅ Tm/ Yb/ Lu/ In/ Ta₂O₅Ta₂O₅ Ta₂O₅ Ta₂O₅ CrO Tm/ Yb/ Lu/ In/ CrO CrO CrO CrO Cr₂O₃ Tm/ Yb/ Lu/In/ Cr₂O₃ Cr₂O₃ Cr₂O₃ Cr₂O₃ CrO₂ Tm/ Yb/ Lu/ In/ CrO₂ CrO₂ CrO₂ CrO₂CrO₃ Tm/ Yb/ Lu/ In/ CrO₃ CrO₃ CrO₃ CrO₃ Cr₈O₂₁ Tm/ Yb/ Lu/ In/ Cr₈O₂₁Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ MoO₂ Tm/ Yb/ Lu/ In/ MoO₂ MoO₂ MoO₂ MoO₂ MoO₃ Tm/Yb/ Lu/ In/ MoO₃ MoO₃ MoO₃ MoO₃ W₂O₃ Tm/ Yb/ Lu/ In/ W₂O₃ W₂O₃ W₂O₃ W₂O₃WoO₂ Tm/ Yb/ Lu/ In/ WoO₂ WoO₂ WoO₂ WoO₂ WoO₃ Tm/ Yb/ Lu/ In/ WoO₃ WoO₃WoO₃ WoO₃ MnO Tm/ Yb/ Lu/ In/ MnO MnO MnO MnO Mn/Mg/O Tm/ Yb/ Lu/ In/Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn₃O₄ Tm/ Yb/ Lu/ In/ Mn₃O₄ Mn₃O₄ Mn₃O₄Mn₃O₄ Mn₂O₃ Tm/ Yb/ Lu/ In/ Mn₂O₃ Mn₂O₃ Mn₂O₃ Mn₂O₃ MnO₂ Tm/ Yb/ Lu/ In/MnO₂ MnO₂ MnO₂ MnO₂ Mn₂O₇ Tm/ Yb/ Lu/ In/ Mn₂O₇ Mn₂O₇ Mn₂O₇ Mn₂O₇ ReO₂Tm/ Yb/ Lu/ In/ ReO₂ ReO₂ ReO₂ ReO₂ ReO₃ Tm/ Yb/ Lu/ In/ ReO₃ ReO₃ ReO₃ReO₃ Re₂O₇ Tm/ Yb/ Lu/ In/ Re₂O₇ Re₂O₇ Re₂O₇ Re₂O₇ Mg₃Mn₃—B₂O₁₀ Tm/ Yb/Lu/ In/ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀ Mg₃(BO₃)₂Tm/ Yb/ Lu/ In/ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂ NaWO₄ Tm/ Yb/Lu/ In/ NaWO₄ NaWO₄ NaWO₄ NaWO₄ Mg₆MnO₈ Tm/ Yb/ Lu/ In/ Mg₆MnO₈ Mg₆MnO₈Mg₆MnO₈ Mg₆MnO₈ Mn₂O₄ Tm/ Yb/ Lu/ In/ Mn₂O₄ Mn₂O₄ Mn₂O₄ Mn₂O₄(Li,Mg)₆MnO₈ Tm/ Yb/ Lu/ In/ (Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈(Li,Mg)₆MnO₈ Na₄P₂O₇ Tm/ Yb/ Lu/ In/ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇Mo₂O₈ Tm/ Yb/ Lu/ In/ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mn₃O₄/WO₄ Tm/ Yb/ Lu/ In/Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Na₂WO₄ Tm/ Yb/ Lu/ In/ Na₂WO₄Na₂WO₄ Na₂WO₄ Na₂WO₄ Zr₂Mo₂O₈ Tm/ Yb/ Lu/ In/ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈Zr₂Mo₂O₈ NaMnO₄—/ Tm/ Yb/ Lu/ In/ MgO NaMnO₄—/ NaMnO₄—/ NaMnO₄—/NaMnO₄—/ MgO MgO MgO MgO Na₁₀Mn—W₅O₁₇ Tm/ Yb/ Lu/ In/ Na₁₀Mn—W₅O₁₇Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ La₃NdO₆ Tm/ Yb/ Lu/ In/ La₃NdO₆La₃NdO₆ La₃NdO₆ La₃NdO₆ LaNd₃O₆ Tm/ Yb/ Lu/ In/ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆LaNd₃O₆ La_(1,5)Nd_(2,5)O₆ Tm/ Yb/ Lu/ In/ La_(1,5)Nd_(2,5)O₆La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆La_(2,5)Nd_(1,5)O₆ Tm/ Yb/ Lu/ In/ La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆ La_(3,2)Nd_(0,8)O₆ Tm/ Yb/ Lu/ In/La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆La_(3,2)Nd_(0,8)O₆ La_(3,5)Nd_(0,5)O₆ Tm/ Yb/ Lu/ In/ La_(3,5)Nd_(0,5)O₆La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆La_(3,8)Nd_(0,2)O₆ Tm/ Yb/ Lu/ In/ La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆ Y—La Tm/ Yb/ Lu/ In/ Y—La Y—LaY—La Y—La Zr—La Tm/ Yb/ Lu/ In/ Zr—La Zr—La Zr—La Zr—La Pr—La Tm/ Yb/Lu/ In/ Pr—La Pr—La Pr—La Pr—La Ce—La Tm/ Yb/ Lu/ In/ Ce—La Ce—La Ce—LaCe—La

TABLE 5 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS (DOP) Dop NW Y Sc AlCu Li₂O Y/ Sc/ Al/ Cu/ Li₂O Li₂O Li₂O Li₂O Na₂O Y/ Sc/ Al/ Cu/ Na₂O Na₂ONa₂O Na₂O K₂O Y/ Sc/ Al/ Cu/ K₂O K₂O K₂O K₂O Rb₂O Y/ Sc/ Al/ Cu/ Rb₂ORb₂O Rb₂O Rb₂O Cs₂O Y/ Sc/ Al/ Cu/ Cs₂O Cs₂O Cs₂O Cs₂O BeO Y/ Sc/ Al/Cu/ BeO BeO BeO BeO MgO Y/ Sc/ Al/ Cu/ MgO MgO MgO MgO CaO Y/ Sc/ Al/Cu/ CaO CaO CaO CaO SrO Y/ Sc/ Al/ Cu/ SrO SrO SrO SrO BaO Y/ Sc/ Al/Cu/ BaO BaO BaO BaO Sc₂O₃ Y/ Sc/ Al/ Cu/ Sc₂O₃ Sc₂O₃ Sc₂O₃ Sc₂O₃ Y₂O₃ Y/Sc/ Al/ Cu/ Y₂O₃ Y₂O₃ Y₂O₃ Y₂O₃ La₂O₃ Y/ Sc/ Al/ Cu/ La₂O₃ La₂O₃ La₂O₃La₂O₃ CeO₂ Y/ Sc/ Al/ Cu/ CeO₂ CeO₂ CeO₂ CeO₂ Ce₂O₃ Y/ Sc/ Al/ Cu/ Ce₂O₃Ce₂O₃ Ce₂O₃ Ce₂O₃ Pr₂O₃ Y/ Sc/ Al/ Cu/ Pr₂O₃ Pr₂O₃ Pr₂O₃ Pr₂O₃ Nd₂O₃ Y/Sc/ Al/ Cu/ Nd₂O₃ Nd₂O₃ Nd₂O₃ Nd₂O₃ Sm₂O₃ Y/ Sc/ Al/ Cu/ Sm₂O₃ Sm₂O₃Sm₂O₃ Sm₂O₃ Eu₂O₃ Y/ Sc/ Al/ Cu/ Eu₂O₃ Eu₂O₃ Eu₂O₃ Eu₂O₃ Gd₂O₃ Y/ Sc/Al/ Cu/ Gd₂O₃ Gd₂O₃ Gd₂O₃ Gd₂O₃ Tb₂O₃ Y/ Sc/ Al/ Cu/ Tb₂O₃ Tb₂O₃ Tb₂O₃Tb₂O₃ TbO₂ Y/ Sc/ Al/ Cu/ TbO₂ TbO₂ TbO₂ TbO₂ Tb₆O₁₁ Y/ Sc/ Al/ Cu/Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Dy₂O₃ Y/ Sc/ Al/ Cu/ Dy₂O₃ Dy₂O₃ Dy₂O₃ Dy₂O₃Ho₂O₃ Y/ Sc/ Al/ Cu/ Ho₂O₃ Ho₂O₃ Ho₂O₃ Ho₂O₃ Er₂O₃ Y/ Sc/ Al/ Cu/ Er₂O₃Er₂O₃ Er₂O₃ Er₂O₃ Tm₂O₃ Y/ Sc/ Al/ Cu/ Tm₂O₃ Tm₂O₃ Tm₂O₃ Tm₂O₃ Yb₂O₃ Y/Sc/ Al/ Cu/ Yb₂O₃ Yb₂O₃ Yb₂O₃ Yb₂O₃ Lu₂O₃ Y/ Sc/ Al/ Cu/ Lu₂O₃ Lu₂O₃Lu₂O₃ Lu₂O₃ Ac₂O₃ Y/ Sc/ Al/ Cu/ Ac₂O₃ Ac₂O₃ Ac₂O₃ Ac₂O₃ Th₂O₃ Y/ Sc/Al/ Cu/ Th₂O₃ Th₂O₃ Th₂O₃ Th₂O₃ ThO₂ Y/ Sc/ Al/ Cu/ ThO₂ ThO₂ ThO₂ ThO₂Pa₂O₃ Y/ Sc/ Al/ Cu/ Pa₂O₃ Pa₂O₃ Pa₂O₃ Pa₂O₃ PaO₂ Y/ Sc/ Al/ Cu/ PaO₂PaO₂ PaO₂ PaO₂ TiO₂ Y/ Sc/ Al/ Cu/ TiO₂ TiO₂ TiO₂ TiO₂ TiO Y/ Sc/ Al/Cu/ TiO TiO TiO TiO Ti₂O₃ Y/ Sc/ Al/ Cu/ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₃O Y/Sc/ Al/ Cu/ Ti₃O Ti₃O Ti₃O Ti₃O Ti₂O Y/ Sc/ Al/ Cu/ Ti₂O Ti₂O Ti₂O Ti₂OTi₃O₅ Y/ Sc/ Al/ Cu/ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₄O₇ Y/ Sc/ Al/ Cu/ Ti₄O₇Ti₄O₇ Ti₄O₇ Ti₄O₇ ZrO₂ Y/ Sc/ Al/ Cu/ ZrO₂ ZrO₂ ZrO₂ ZrO₂ HfO₂ Y/ Sc/Al/ Cu/ HfO₂ HfO₂ HfO₂ HfO₂ VO Y/ Sc/ Al/ Cu/ VO VO VO VO V₂O₃ Y/ Sc/Al/ Cu/ V₂O₃ V₂O₃ V₂O₃ V₂O₃ VO₂ Y/ Sc/ Al/ Cu/ VO₂ VO₂ VO₂ VO₂ V₂O₅ Y/Sc/ Al/ Cu/ V₂O₅ V₂O₅ V₂O₅ V₂O₅ V₃O₇ Y/ Sc/ Al/ Cu/ V₃O₇ V₃O₇ V₃O₇ V₃O₇V₄O₉ Y/ Sc/ Al/ Cu/ V₄O₉ V₄O₉ V₄O₉ V₄O₉ V₆O₁₃ Y/ Sc/ Al/ Cu/ V₆O₁₃ V₆O₁₃V₆O₁₃ V₆O₁₃ NbO Y/ Sc/ Al/ Cu/ NbO NbO NbO NbO NbO₂ Y/ Sc/ Al/ Cu/ NbO₂NbO₂ NbO₂ NbO₂ Nb₂O₅ Y/ Sc/ Al/ Cu/ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₈O₁₉ Y/Sc/ Al/ Cu/ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₁₆O₃₈ Y/ Sc/ Al/ Cu/ Nb₁₆O₃₈Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₂O₂₉ Y/ Sc/ Al/ Cu/ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉Nb₁₂O₂₉ Nb₄₇O₁₁₆ Y/ Sc/ Al/ Cu/ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆Ta₂O₅ Y/ Sc/ Al/ Cu/ Ta₂O₅ Ta₂O₅ Ta₂O₅ Ta₂O₅ CrO Y/ Sc/ Al/ Cu/ CrO CrOCrO CrO Cr₂O₃ Y/ Sc/ Al/ Cu/ Cr₂O₃ Cr₂O₃ Cr₂O₃ Cr₂O₃ CrO₂ Y/ Sc/ Al/ Cu/CrO₂ CrO₂ CrO₂ CrO₂ CrO₃ Y/ Sc/ Al/ Cu/ CrO₃ CrO₃ CrO₃ CrO₃ Cr₈O₂₁ Y/Sc/ Al/ Cu/ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ MoO₂ Y/ Sc/ Al/ Cu/ MoO₂ MoO₂MoO₂ MoO₂ MoO₃ Y/ Sc/ Al/ Cu/ MoO₃ MoO₃ MoO₃ MoO₃ W₂O₃ Y/ Sc/ Al/ Cu/W₂O₃ W₂O₃ W₂O₃ W₂O₃ WoO₂ Y/ Sc/ Al/ Cu/ WoO₂ WoO₂ WoO₂ WoO₂ WoO₃ Y/ Sc/Al/ Cu/ WoO₃ WoO₃ WoO₃ WoO₃ MnO Y/ Sc/ Al/ Cu/ MnO MnO MnO MnO Mn/Mg/OY/ Sc/ Al/ Cu/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn₃O₄ Y/ Sc/ Al/ Cu/Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₂O₃ Y/ Sc/ Al/ Cu/ Mn₂O₃ Mn₂O₃ Mn₂O₃ Mn₂O₃MnO₂ Y/ Sc/ Al/ Cu/ MnO₂ MnO₂ MnO₂ MnO₂ Mn₂O₇ Y/ Sc/ Al/ Cu/ Mn₂O₇ Mn₂O₇Mn₂O₇ Mn₂O₇ ReO₂ Y/ Sc/ Al/ Cu/ ReO₂ ReO₂ ReO₂ ReO₂ ReO₃ Y/ Sc/ Al/ Cu/ReO₃ ReO₃ ReO₃ ReO₃ Re₂O₇ Y/ Sc/ Al/ Cu/ Re₂O₇ Re₂O₇ Re₂O₇ Re₂O₇Mg₃Mn₃—B₂O₁₀ Y/ Sc/ Al/ Cu/ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀Mg₃Mn₃—B₂O₁₀ Mg₃(BO₃)₂ Y/ Sc/ Al/ Cu/ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂Mg₃(BO₃)₂ NaWO₄ Y/ Sc/ Al/ Cu/ NaWO₄ NaWO₄ NaWO₄ NaWO₄ Mg₆MnO₈ Y/ Sc/Al/ Cu/ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mn₂O₄ Y/ Sc/ Al/ Cu/ Mn₂O₄ Mn₂O₄Mn₂O₄ Mn₂O₄ (Li,Mg)₆MnO₈ Y/ Sc/ Al/ Cu/ (Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈(Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ Na₄P₂O₇ Y/ Sc/ Al/ Cu/ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇Na₄P₂O₇ Mo₂O₈ Y/ Sc/ Al/ Cu/ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mn₃O₄/WO₄ Y/ Sc/Al/ Cu/ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Na₂WO₄ Y/ Sc/ Al/ Cu/Na₂WO₄ Na₂WO₄ Na₂WO₄ Na₂WO₄ Zr₂Mo₂O₈ Y/ Sc/ Al/ Cu/ Zr₂Mo₂O₈ Zr₂Mo₂O₈Zr₂Mo₂O₈ Zr₂Mo₂O₈ NaMnO₄—/ Y/ Sc/ Al/ Cu/ MgO NaMnO₄—/ NaMnO₄—/ NaMnO₄—/NaMnO₄—/ MgO MgO MgO MgO Na₁₀Mn—W₅O₁₇ Y/ Sc/ Al/ Cu/ Na₁₀Mn—W₅O₁₇Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ La₃NdO₆ Y/ Sc/ Al/ Cu/ La₃NdO₆La₃NdO₆ La₃NdO₆ La₃NdO₆ LaNd₃O₆ Y/ Sc/ Al/ Cu/ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆LaNd₃O₆ La_(1,5)Nd_(2,5)O₆ Y/ Sc/ Al/ Cu/ La_(1,5)Nd_(2,5)O₆La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆La_(2,5)Nd_(1,5)O₆ Y/ Sc/ Al/ Cu/ La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆ La_(3,2)Nd_(0,8)O₆ Y/ Sc/ Al/ Cu/La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆La_(3,2)Nd_(0,8)O₆ La_(3,5)Nd_(0,5)O₆ Y/ Sc/ Al/ Cu/ La_(3,5)Nd_(0,5)O₆La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆La_(3,8)Nd_(0,2)O₆ Y/ Sc/ Al/ Cu/ La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆ Y—La Y/ Sc/ Al/ Cu/ Y—La Y—La Y—LaY—La Zr—La Y/ Sc/ Al/ Cu/ Zr—La Zr—La Zr—La Zr—La Pr—La Y/ Sc/ Al/ Cu/Pr—La Pr—La Pr—La Pr—La Ce—La Y/ Sc/ Al/ Cu/ Ce—La Ce—La Ce—La Ce—La DopNW Ga Hf Fe Cr Li₂O Ga/ Hf/ Fe/ Cr/ Li₂O Li₂O Li₂O Li₂O Na₂O Ga/ Hf/ Fe/Cr/ Na₂O Na₂O Na₂O Na₂O K₂O Ga/ Hf/ Fe/ Cr/ K₂O K₂O K₂O K₂O Rb₂O Ga/ Hf/Fe/ Cr/ Rb₂O Rb₂O Rb₂O Rb₂O Cs₂O Ga/ Hf/ Fe/ Cr/ Cs₂O Cs₂O Cs₂O Cs₂O BeOGa/ Hf/ Fe/ Cr/ BeO BeO BeO BeO MgO Ga/ Hf/ Fe/ Cr/ MgO MgO MgO MgO CaOGa/ Hf/ Fe/ Cr/ CaO CaO CaO CaO SrO Ga/ Hf/ Fe/ Cr/ SrO SrO SrO SrO BaOGa/ Hf/ Fe/ Cr/ BaO BaO BaO BaO Sc₂O₃ Ga/ Hf/ Fe/ Cr/ Sc₂O₃ Sc₂O₃ Sc₂O₃Sc₂O₃ Y₂O₃ Ga/ Hf/ Fe/ Cr/ Y₂O₃ Y₂O₃ Y₂O₃ Y₂O₃ La₂O₃ Ga/ Hf/ Fe/ Cr/La₂O₃ La₂O₃ La₂O₃ La₂O₃ CeO₂ Ga/ Hf/ Fe/ Cr/ CeO₂ CeO₂ CeO₂ CeO₂ Ce₂O₃Ga/ Hf/ Fe/ Cr/ Ce₂O₃ Ce₂O₃ Ce₂O₃ Ce₂O₃ Pr₂O₃ Ga/ Hf/ Fe/ Cr/ Pr₂O₃Pr₂O₃ Pr₂O₃ Pr₂O₃ Nd₂O₃ Ga/ Hf/ Fe/ Cr/ Nd₂O₃ Nd₂O₃ Nd₂O₃ Nd₂O₃ Sm₂O₃Ga/ Hf/ Fe/ Cr/ Sm₂O₃ Sm₂O₃ Sm₂O₃ Sm₂O₃ Eu₂O₃ Ga/ Hf/ Fe/ Cr/ Eu₂O₃Eu₂O₃ Eu₂O₃ Eu₂O₃ Gd₂O₃ Ga/ Hf/ Fe/ Cr/ Gd₂O₃ Gd₂O₃ Gd₂O₃ Gd₂O₃ Tb₂O₃Ga/ Hf/ Fe/ Cr/ Tb₂O₃ Tb₂O₃ Tb₂O₃ Tb₂O₃ TbO₂ Ga/ Hf/ Fe/ Cr/ TbO₂ TbO₂TbO₂ TbO₂ Tb₆O₁₁ Ga/ Hf/ Fe/ Cr/ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Dy₂O₃ Ga/Hf/ Fe/ Cr/ Dy₂O₃ Dy₂O₃ Dy₂O₃ Dy₂O₃ Ho₂O₃ Ga/ Hf/ Fe/ Cr/ Ho₂O₃ Ho₂O₃Ho₂O₃ Ho₂O₃ Er₂O₃ Ga/ Hf/ Fe/ Cr/ Er₂O₃ Er₂O₃ Er₂O₃ Er₂O₃ Tm₂O₃ Ga/ Hf/Fe/ Cr/ Tm₂O₃ Tm₂O₃ Tm₂O₃ Tm₂O₃ Yb₂O₃ Ga/ Hf/ Fe/ Cr/ Yb₂O₃ Yb₂O₃ Yb₂O₃Yb₂O₃ Lu₂O₃ Ga/ Hf/ Fe/ Cr/ Lu₂O₃ Lu₂O₃ Lu₂O₃ Lu₂O₃ Ac₂O₃ Ga/ Hf/ Fe/Cr/ Ac₂O₃ Ac₂O₃ Ac₂O₃ Ac₂O₃ Th₂O₃ Ga/ Hf/ Fe/ Cr/ Th₂O₃ Th₂O₃ Th₂O₃Th₂O₃ ThO₂ Ga/ Hf/ Fe/ Cr/ ThO₂ ThO₂ ThO₂ ThO₂ Pa₂O₃ Ga/ Hf/ Fe/ Cr/Pa₂O₃ Pa₂O₃ Pa₂O₃ Pa₂O₃ PaO₂ Ga/ Hf/ Fe/ Cr/ PaO₂ PaO₂ PaO₂ PaO₂ TiO₂Ga/ Hf/ Fe/ Cr/ TiO₂ TiO₂ TiO₂ TiO₂ TiO Ga/ Hf/ Fe/ Cr/ TiO TiO TiO TiOTi₂O₃ Ga/ Hf/ Fe/ Cr/ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₃O Ga/ Hf/ Fe/ Cr/ Ti₃OTi₃O Ti₃O Ti₃O Ti₂O Ga/ Hf/ Fe/ Cr/ Ti₂O Ti₂O Ti₂O Ti₂O Ti₃O₅ Ga/ Hf/Fe/ Cr/ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₄O₇ Ga/ Hf/ Fe/ Cr/ Ti₄O₇ Ti₄O₇ Ti₄O₇Ti₄O₇ ZrO₂ Ga/ Hf/ Fe/ Cr/ ZrO₂ ZrO₂ ZrO₂ ZrO₂ HfO₂ Ga/ Hf/ Fe/ Cr/ HfO₂HfO₂ HfO₂ HfO₂ VO Ga/ Hf/ Fe/ Cr/ VO VO VO VO V₂O₃ Ga/ Hf/ Fe/ Cr/ V₂O₃V₂O₃ V₂O₃ V₂O₃ VO₂ Ga/ Hf/ Fe/ Cr/ VO₂ VO₂ VO₂ VO₂ V₂O₅ Ga/ Hf/ Fe/ Cr/V₂O₅ V₂O₅ V₂O₅ V₂O₅ V₃O₇ Ga/ Hf/ Fe/ Cr/ V₃O₇ V₃O₇ V₃O₇ V₃O₇ V₄O₉ Ga/Hf/ Fe/ Cr/ V₄O₉ V₄O₉ V₄O₉ V₄O₉ V₆O₁₃ Ga/ Hf/ Fe/ Cr/ V₆O₁₃ V₆O₁₃ V₆O₁₃V₆O₁₃ NbO Ga/ Hf/ Fe/ Cr/ NbO NbO NbO NbO NbO₂ Ga/ Hf/ Fe/ Cr/ NbO₂ NbO₂NbO₂ NbO₂ Nb₂O₅ Ga/ Hf/ Fe/ Cr/ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₈O₁₉ Ga/ Hf/Fe/ Cr/ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₁₆O₃₈ Ga/ Hf/ Fe/ Cr/ Nb₁₆O₃₈Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₂O₂₉ Ga/ Hf/ Fe/ Cr/ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉Nb₁₂O₂₉ Nb₄₇O₁₁₆ Ga/ Hf/ Fe/ Cr/ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆Ta₂O₅ Ga/ Hf/ Fe/ Cr/ Ta₂O₅ Ta₂O₅ Ta₂O₅ Ta₂O₅ CrO Ga/ Hf/ Fe/ Cr/ CrOCrO CrO CrO Cr₂O₃ Ga/ Hf/ Fe/ Cr/ Cr₂O₃ Cr₂O₃ Cr₂O₃ Cr₂O₃ CrO₂ Ga/ Hf/Fe/ Cr/ CrO₂ CrO₂ CrO₂ CrO₂ CrO₃ Ga/ Hf/ Fe/ Cr/ CrO₃ CrO₃ CrO₃ CrO₃Cr₈O₂₁ Ga/ Hf/ Fe/ Cr/ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ MoO₂ Ga/ Hf/ Fe/ Cr/MoO₂ MoO₂ MoO₂ MoO₂ MoO₃ Ga/ Hf/ Fe/ Cr/ MoO₃ MoO₃ MoO₃ MoO₃ W₂O₃ Ga/Hf/ Fe/ Cr/ W₂O₃ W₂O₃ W₂O₃ W₂O₃ WoO₂ Ga/ Hf/ Fe/ Cr/ WoO₂ WoO₂ WoO₂ WoO₂WoO₃ Ga/ Hf/ Fe/ Cr/ WoO₃ WoO₃ WoO₃ WoO₃ MnO Ga/ Hf/ Fe/ Cr/ MnO MnO MnOMnO Mn/Mg/O Ga/ Hf/ Fe/ Cr/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn₃O₄ Ga/Hf/ Fe/ Cr/ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₂O₃ Ga/ Hf/ Fe/ Cr/ Mn₂O₃ Mn₂O₃Mn₂O₃ Mn₂O₃ MnO₂ Ga/ Hf/ Fe/ Cr/ MnO₂ MnO₂ MnO₂ MnO₂ Mn₂O₇ Ga/ Hf/ Fe/Cr/ Mn₂O₇ Mn₂O₇ Mn₂O₇ Mn₂O₇ ReO₂ Ga/ Hf/ Fe/ Cr/ ReO₂ ReO₂ ReO₂ ReO₂ReO₃ Ga/ Hf/ Fe/ Cr/ ReO₃ ReO₃ ReO₃ ReO₃ Re₂O₇ Ga/ Hf/ Fe/ Cr/ Re₂O₇Re₂O₇ Re₂O₇ Re₂O₇ Mg₃Mn₃—B₂O₁₀ Ga/ Hf/ Fe/ Cr/ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀ Mg₃(BO₃)₂ Ga/ Hf/ Fe/ Cr/ Mg₃(BO₃)₂ Mg₃(BO₃)₂Mg₃(BO₃)₂ Mg₃(BO₃)₂ NaWO₄ Ga/ Hf/ Fe/ Cr/ NaWO₄ NaWO₄ NaWO₄ NaWO₄Mg₆MnO₈ Ga/ Hf/ Fe/ Cr/ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mn₂O₄ Ga/ Hf/Fe/ Cr/ Mn₂O₄ Mn₂O₄ Mn₂O₄ Mn₂O₄ (Li,Mg)₆MnO₈ Ga/ Hf/ Fe/ Cr/(Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ Na₄P₂O₇ Ga/ Hf/ Fe/Cr/ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Mo₂O₈ Ga/ Hf/ Fe/ Cr/ Mo₂O₈ Mo₂O₈Mo₂O₈ Mo₂O₈ Mn₃O₄/WO₄ Ga/ Hf/ Fe/ Cr/ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄Mn₃O₄/WO₄ Na₂WO₄ Ga/ Hf/ Fe/ Cr/ Na₂WO₄ Na₂WO₄ Na₂WO₄ Na₂WO₄ Zr₂Mo₂O₈Ga/ Hf/ Fe/ Cr/ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ NaMnO₄—/ Ga/ Hf/ Fe/Cr/ MgO NaMnO₄—/ NaMnO₄—/ NaMnO₄—/ NaMnO₄—/ MgO MgO MgO MgO Na₁₀Mn—W₅O₁₇Ga/ Hf/ Fe/ Cr/ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇La₃NdO₆ Ga/ Hf/ Fe/ Cr/ La₃NdO₆ La₃NdO₆ La₃NdO₆ La₃NdO₆ LaNd₃O₆ Ga/ Hf/Fe/ Cr/ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆ La_(1,5)Nd_(2,5)O₆ Ga/ Hf/ Fe/Cr/ La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆La_(1,5)Nd_(2,5)O₆ La_(2,5)Nd_(1,5)O₆ Ga/ Hf/ Fe/ Cr/ La_(2,5)Nd_(1,5)O₆La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆La_(3,2)Nd_(0,8)O₆ Ga/ Hf/ Fe/ Cr/ La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆ La_(3,5)Nd_(0,5)O₆ Ga/ Hf/ Fe/ Cr/La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆La_(3,5)Nd_(0,5)O₆ La_(3,8)Nd_(0,2)O₆ Ga/ Hf/ Fe/ Cr/ La_(3,8)Nd_(0,2)O₆La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆ Y—La Ga/ Hf/Fe/ Cr/ Y—La Y—La Y—La Y—La Zr—La Ga/ Hf/ Fe/ Cr/ Zr—La Zr—La Zr—LaZr—La Pr—La Ga/ Hf/ Fe/ Cr/ Pr—La Pr—La Pr—La Pr—La Ce—La Ga/ Hf/ Fe/Cr/ Ce—La Ce—La Ce—La Ce—La

TABLE 6 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS (DOP) Dop NW Ru Zr TaRh Li₂O Ru/ Zr/ Ta/ Rh/ Li₂O Li₂O Li₂O Li₂O Na₂O Ru/ Zr/ Ta/ Rh/ Na₂ONa₂O Na₂O Na₂O K₂O Ru/ Zr/ Ta/ Rh/ K₂O K₂O K₂O K₂O Rb₂O Ru/ Zr/ Ta/ Rh/Rb₂O Rb₂O Rb₂O Rb₂O Cs₂O Ru/ Zr/ Ta/ Rh/ Cs₂O Cs₂O Cs₂O Cs₂O BeO Ru/ Zr/Ta/ Rh/ BeO BeO BeO BeO MgO Ru/ Zr/ Ta/ Rh/ MgO MgO MgO MgO CaO Ru/ Zr/Ta/ Rh/ CaO CaO CaO CaO SrO Ru/ Zr/ Ta/ Rh/ SrO SrO SrO SrO BaO Ru/ Zr/Ta/ Rh/ BaO BaO BaO BaO Sc₂O₃ Ru/ Zr/ Ta/ Rh/ Sc₂O₃ Sc₂O₃ Sc₂O₃ Sc₂O₃Y₂O₃ Ru/ Zr/ Ta/ Rh/ Y₂O₃ Y₂O₃ Y₂O₃ Y₂O₃ La₂O₃ Ru/ Zr/ Ta/ Rh/ La₂O₃La₂O₃ La₂O₃ La₂O₃ CeO₂ Ru/ Zr/ Ta/ Rh/ CeO₂ CeO₂ CeO₂ CeO₂ Ce₂O₃ Ru/ Zr/Ta/ Rh/ Ce₂O₃ Ce₂O₃ Ce₂O₃ Ce₂O₃ Pr₂O₃ Ru/ Zr/ Ta/ Rh/ Pr₂O₃ Pr₂O₃ Pr₂O₃Pr₂O₃ Nd₂O₃ Ru/ Zr/ Ta/ Rh/ Nd₂O₃ Nd₂O₃ Nd₂O₃ Nd₂O₃ Sm₂O₃ Ru/ Zr/ Ta/Rh/ Sm₂O₃ Sm₂O₃ Sm₂O₃ Sm₂O₃ Eu₂O₃ Ru/ Zr/ Ta/ Rh/ Eu₂O₃ Eu₂O₃ Eu₂O₃Eu₂O₃ Gd₂O₃ Ru/ Zr/ Ta/ Rh/ Gd₂O₃ Gd₂O₃ Gd₂O₃ Gd₂O₃ Tb₂O₃ Ru/ Zr/ Ta/Rh/ Tb₂O₃ Tb₂O₃ Tb₂O₃ Tb₂O₃ TbO₂ Ru/ Zr/ Ta/ Rh/ TbO₂ TbO₂ TbO₂ TbO₂Tb₆O₁₁ Ru/ Zr/ Ta/ Rh/ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Dy₂O₃ Ru/ Zr/ Ta/ Rh/Dy₂O₃ Dy₂O₃ Dy₂O₃ Dy₂O₃ Ho₂O₃ Ru/ Zr/ Ta/ Rh/ Ho₂O₃ Ho₂O₃ Ho₂O₃ Ho₂O₃Er₂O₃ Ru/ Zr/ Ta/ Rh/ Er₂O₃ Er₂O₃ Er₂O₃ Er₂O₃ Tm₂O₃ Ru/ Zr/ Ta/ Rh/Tm₂O₃ Tm₂O₃ Tm₂O₃ Tm₂O₃ Yb₂O₃ Ru/ Zr/ Ta/ Rh/ Yb₂O₃ Yb₂O₃ Yb₂O₃ Yb₂O₃Lu₂O₃ Ru/ Zr/ Ta/ Rh/ Lu₂O₃ Lu₂O₃ Lu₂O₃ Lu₂O₃ Ac₂O₃ Ru/ Zr/ Ta/ Rh/Ac₂O₃ Ac₂O₃ Ac₂O₃ Ac₂O₃ Th₂O₃ Ru/ Zr/ Ta/ Rh/ Th₂O₃ Th₂O₃ Th₂O₃ Th₂O₃ThO₂ Ru/ Zr/ Ta/ Rh/ ThO₂ ThO₂ ThO₂ ThO₂ Pa₂O₃ Ru/ Zr/ Ta/ Rh/ Pa₂O₃Pa₂O₃ Pa₂O₃ Pa₂O₃ PaO₂ Ru/ Zr/ Ta/ Rh/ PaO₂ PaO₂ PaO₂ PaO₂ TiO₂ Ru/ Zr/Ta/ Rh/ TiO₂ TiO₂ TiO₂ TiO₂ TiO Ru/ Zr/ Ta/ Rh/ TiO TiO TiO TiO Ti₂O₃Ru/ Zr/ Ta/ Rh/ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₃O Ru/ Zr/ Ta/ Rh/ Ti₃O Ti₃OTi₃O Ti₃O Ti₂O Ru/ Zr/ Ta/ Rh/ Ti₂O Ti₂O Ti₂O Ti₂O Ti₃O₅ Ru/ Zr/ Ta/ Rh/Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₄O₇ Ru/ Zr/ Ta/ Rh/ Ti₄O₇ Ti₄O₇ Ti₄O₇ Ti₄O₇ZrO₂ Ru/ Zr/ Ta/ Rh/ ZrO₂ ZrO₂ ZrO₂ ZrO₂ HfO₂ Ru/ Zr/ Ta/ Rh/ HfO₂ HfO₂HfO₂ HfO₂ VO Ru/ Zr/ Ta/ Rh/ VO VO VO VO V₂O₃ Ru/ Zr/ Ta/ Rh/ V₂O₃ V₂O₃V₂O₃ V₂O₃ VO₂ Ru/ Zr/ Ta/ Rh/ VO₂ VO₂ VO₂ VO₂ V₂O₅ Ru/ Zr/ Ta/ Rh/ V₂O₅V₂O₅ V₂O₅ V₂O₅ V₃O₇ Ru/ Zr/ Ta/ Rh/ V₃O₇ V₃O₇ V₃O₇ V₃O₇ V₄O₉ Ru/ Zr/ Ta/Rh/ V₄O₉ V₄O₉ V₄O₉ V₄O₉ V₆O₁₃ Ru/ Zr/ Ta/ Rh/ V₆O₁₃ V₆O₁₃ V₆O₁₃ V₆O₁₃NbO Ru/ Zr/ Ta/ Rh/ NbO NbO NbO NbO NbO₂ Ru/ Zr/ Ta/ Rh/ NbO₂ NbO₂ NbO₂NbO₂ Nb₂O₅ Ru/ Zr/ Ta/ Rh/ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₈O₁₉ Ru/ Zr/ Ta/Rh/ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₁₆O₃₈ Ru/ Zr/ Ta/ Rh/ Nb₁₆O₃₈ Nb₁₆O₃₈Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₂O₂₉ Ru/ Zr/ Ta/ Rh/ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉Nb₄₇O₁₁₆ Ru/ Zr/ Ta/ Rh/ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Ta₂O₅ Ru/Zr/ Ta/ Rh/ Ta₂O₅ Ta₂O₅ Ta₂O₅ Ta₂O₅ CrO Ru/ Zr/ Ta/ Rh/ CrO CrO CrO CrOCr₂O₃ Ru/ Zr/ Ta/ Rh/ Cr₂O₃ Cr₂O₃ Cr₂O₃ Cr₂O₃ CrO₂ Ru/ Zr/ Ta/ Rh/ CrO₂CrO₂ CrO₂ CrO₂ CrO₃ Ru/ Zr/ Ta/ Rh/ CrO₃ CrO₃ CrO₃ CrO₃ Cr₈O₂₁ Ru/ Zr/Ta/ Rh/ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ MoO₂ Ru/ Zr/ Ta/ Rh/ MoO₂ MoO₂ MoO₂MoO₂ MoO₃ Ru/ Zr/ Ta/ Rh/ MoO₃ MoO₃ MoO₃ MoO₃ W₂O₃ Ru/ Zr/ Ta/ Rh/ W₂O₃W₂O₃ W₂O₃ W₂O₃ WoO₂ Ru/ Zr/ Ta/ Rh/ WoO₂ WoO₂ WoO₂ WoO₂ WoO₃ Ru/ Zr/ Ta/Rh/ WoO₃ WoO₃ WoO₃ WoO₃ MnO Ru/ Zr/ Ta/ Rh/ MnO MnO MnO MnO Mn/Mg/O Ru/Zr/ Ta/ Rh/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn₃O₄ Ru/ Zr/ Ta/ Rh/ Mn₃O₄Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₂O₃ Ru/ Zr/ Ta/ Rh/ Mn₂O₃ Mn₂O₃ Mn₂O₃ Mn₂O₃ MnO₂ Ru/Zr/ Ta/ Rh/ MnO₂ MnO₂ MnO₂ MnO₂ Mn₂O₇ Ru/ Zr/ Ta/ Rh/ Mn₂O₇ Mn₂O₇ Mn₂O₇Mn₂O₇ ReO₂ Ru/ Zr/ Ta/ Rh/ ReO₂ ReO₂ ReO₂ ReO₂ ReO₃ Ru/ Zr/ Ta/ Rh/ ReO₃ReO₃ ReO₃ ReO₃ Re₂O₇ Ru/ Zr/ Ta/ Rh/ Re₂O₇ Re₂O₇ Re₂O₇ Re₂O₇Mg₃Mn₃—B₂O₁₀ Ru/ Zr/ Ta/ Rh/ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀Mg₃Mn₃—B₂O₁₀ Mg₃(BO₃)₂ Ru/ Zr/ Ta/ Rh/ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂Mg₃(BO₃)₂ NaWO₄ Ru/ Zr/ Ta/ Rh/ NaWO₄ NaWO₄ NaWO₄ NaWO₄ Mg₆MnO₈ Ru/ Zr/Ta/ Rh/ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mn₂O₄ Ru/ Zr/ Ta/ Rh/ Mn₂O₄Mn₂O₄ Mn₂O₄ Mn₂O₄ (Li,Mg)₆—MnO₈ Ru/ Zr/ Ta/ Rh/ (Li,Mg)₆—MnO₈(Li,Mg)₆—MnO₈ (Li,Mg)₆—MnO₈ (Li,Mg)₆—MnO₈ Na₄P₂O₇ Ru/ Zr/ Ta/ Rh/Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Mo₂O₈ Ru/ Zr/ Ta/ Rh/ Mo₂O₈ Mo₂O₈ Mo₂O₈Mo₂O₈ Mn₃O₄/WO₄ Ru/ Zr/ Ta/ Rh/ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄Na₂WO₄ Ru/ Zr/ Ta/ Rh/ Na₂WO₄ Na₂WO₄ Na₂WO₄ Na₂WO₄ Zr₂Mo₂O₈ Ru/ Zr/ Ta/Rh/ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ NaMnO₄—/ Ru/ Zr/ Ta/ Rh/ MgONaMnO₄—/ NaMnO₄—/ NaMnO₄—/ NaMnO₄—/ MgO MgO MgO MgO Na₁₀Mn—W₅O₁₇ Ru/ Zr/Ta/ Rh/ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ La₃NdO₆ Ru/Zr/ Ta/ Rh/ La₃NdO₆ La₃NdO₆ La₃NdO₆ La₃NdO₆ LaNd₃O₆ Ru/ Zr/ Ta/ Rh/LaNd₃O₆ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆ La_(1,5)Nd_(2,5)O₆ Ru/ Zr/ Ta/ Rh/La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆La_(1,5)Nd_(2,5)O₆ La_(2,5)Nd_(1,5)O₆ Ru/ Zr/ Ta/ Rh/ La_(2,5)Nd_(1,5)O₆La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆La_(3,2)Nd_(0,8)O₆ Ru/ Zr/ Ta/ Rh/ La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆ La_(3,5)Nd_(0,5)O₆ Ru/ Zr/ Ta/ Rh/La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆La_(3,5)Nd_(0,5)O₆ La_(3,8)Nd_(0,2)O₆ Ru/ Zr/ Ta/ Rh/ La_(3,8)Nd_(0,2)O₆La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆ Y—La Ru/ Zr/Ta/ Rh/ Y—La Y—La Y—La Y—La Zr—La Ru/ Zr/ Ta/ Rh/ Zr—La Zr—La Zr—LaZr—La Pr—La Ru/ Zr/ Ta/ Rh/ Pr—La Pr—La Pr—La Pr—La Ce—La Ru/ Zr/ Ta/Rh/ Ce—La Ce—La Ce—La Ce—La Dop NW Au Mo Ni Li₂O Au/ Mo/ Ni/ Li₂O Li₂OLi₂O Na₂O Au/ Mo/ Ni/ Na₂O Na₂O Na₂O K₂O Au/ Mo/ Ni/ K₂O K₂O K₂O Rb₂OAu/ Mo/ Ni/ Rb₂O Rb₂O Rb₂O Cs₂O Au/ Mo/ Ni/ Cs₂O Cs₂O Cs₂O BeO Au/ Mo/Ni/ BeO BeO BeO MgO Au/ Mo/ Ni/ MgO MgO MgO CaO Au/ Mo/ Ni/ CaO CaO CaOSrO Au/ Mo/ Ni/ SrO SrO SrO BaO Au/ Mo/ Ni/ BaO BaO BaO Sc₂O₃ Au/ Mo/Ni/ Sc₂O₃ Sc₂O₃ Sc₂O₃ Y₂O₃ Au/ Mo/ Ni/ Y₂O₃ Y₂O₃ Y₂O₃ La₂O₃ Au/ Mo/ Ni/La₂O₃ La₂O₃ La₂O₃ CeO₂ Au/ Mo/ Ni/ CeO₂ CeO₂ CeO₂ Ce₂O₃ Au/ Mo/ Ni/Ce₂O₃ Ce₂O₃ Ce₂O₃ Pr₂O₃ Au/ Mo/ Ni/ Pr₂O₃ Pr₂O₃ Pr₂O₃ Nd₂O₃ Au/ Mo/ Ni/Nd₂O₃ Nd₂O₃ Nd₂O₃ Sm₂O₃ Au/ Mo/ Ni/ Sm₂O₃ Sm₂O₃ Sm₂O₃ Eu₂O₃ Au/ Mo/ Ni/Eu₂O₃ Eu₂O₃ Eu₂O₃ Gd₂O₃ Au/ Mo/ Ni/ Gd₂O₃ Gd₂O₃ Gd₂O₃ Tb₂O₃ Au/ Mo/ Ni/Tb₂O₃ Tb₂O₃ Tb₂O₃ TbO₂ Au/ Mo/ Ni/ TbO₂ TbO₂ TbO₂ Tb₆O₁₁ Au/ Mo/ Ni/Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Dy₂O₃ Au/ Mo/ Ni/ Dy₂O₃ Dy₂O₃ Dy₂O₃ Ho₂O₃ Au/ Mo/Ni/ Ho₂O₃ Ho₂O₃ Ho₂O₃ Er₂O₃ Au/ Mo/ Ni/ Er₂O₃ Er₂O₃ Er₂O₃ Tm₂O₃ Au/ Mo/Ni/ Tm₂O₃ Tm₂O₃ Tm₂O₃ Yb₂O₃ Au/ Mo/ Ni/ Yb₂O₃ Yb₂O₃ Yb₂O₃ Lu₂O₃ Au/ Mo/Ni/ Lu₂O₃ Lu₂O₃ Lu₂O₃ Ac₂O₃ Au/ Mo/ Ni/ Ac₂O₃ Ac₂O₃ Ac₂O₃ Th₂O₃ Au/ Mo/Ni/ Th₂O₃ Th₂O₃ Th₂O₃ ThO₂ Au/ Mo/ Ni/ ThO₂ ThO₂ ThO₂ Pa₂O₃ Au/ Mo/ Ni/Pa₂O₃ Pa₂O₃ Pa₂O₃ PaO₂ Au/ Mo/ Ni/ PaO₂ PaO₂ PaO₂ TiO₂ Au/ Mo/ Ni/ TiO₂TiO₂ TiO₂ TiO Au/ Mo/ Ni/ TiO TiO TiO Ti₂O₃ Au/ Mo/ Ni/ Ti₂O₃ Ti₂O₃Ti₂O₃ Ti₃O Au/ Mo/ Ni/ Ti₃O Ti₃O Ti₃O Ti₂O Au/ Mo/ Ni/ Ti₂O Ti₂O Ti₂OTi₃O₅ Au/ Mo/ Ni/ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₄O₇ Au/ Mo/ Ni/ Ti₄O₇ Ti₄O₇ Ti₄O₇ZrO₂ Au/ Mo/ Ni/ ZrO₂ ZrO₂ ZrO₂ HfO₂ Au/ Mo/ Ni/ HfO₂ HfO₂ HfO₂ VO Au/Mo/ Ni/ VO VO VO V₂O₃ Au/ Mo/ Ni/ V₂O₃ V₂O₃ V₂O₃ VO₂ Au/ Mo/ Ni/ VO₂ VO₂VO₂ V₂O₅ Au/ Mo/ Ni/ V₂O₅ V₂O₅ V₂O₅ V₃O₇ Au/ Mo/ Ni/ V₃O₇ V₃O₇ V₃O₇ V₄O₉Au/ Mo/ Ni/ V₄O₉ V₄O₉ V₄O₉ V₆O₁₃ Au/ Mo/ Ni/ V₆O₁₃ V₆O₁₃ V₆O₁₃ NbO Au/Mo/ Ni/ NbO NbO NbO NbO₂ Au/ Mo/ Ni/ NbO₂ NbO₂ NbO₂ Nb₂O₅ Au/ Mo/ Ni/Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₈O₁₉ Au/ Mo/ Ni/ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₁₆O₃₈ Au/Mo/ Ni/ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₂O₂₉ Au/ Mo/ Ni/ Nb₁₂O₂₉ Nb₁₂O₂₉Nb₁₂O₂₉ Nb₄₇O₁₁₆ Au/ Mo/ Ni/ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Ta₂O₅ Au/ Mo/Ni/ Ta₂O₅ Ta₂O₅ Ta₂O₅ CrO Au/ Mo/ Ni/ CrO CrO CrO Cr₂O₃ Au/ Mo/ Ni/Cr₂O₃ Cr₂O₃ Cr₂O₃ CrO₂ Au/ Mo/ Ni/ CrO₂ CrO₂ CrO₂ CrO₃ Au/ Mo/ Ni/ CrO₃CrO₃ CrO₃ Cr₈O₂₁ Au/ Mo/ Ni/ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ MoO₂ Au/ Mo/ Ni/ MoO₂MoO₂ MoO₂ MoO₃ Au/ Mo/ Ni/ MoO₃ MoO₃ MoO₃ W₂O₃ Au/ Mo/ Ni/ W₂O₃ W₂O₃W₂O₃ WoO₂ Au/ Mo/ Ni/ WoO₂ WoO₂ WoO₂ WoO₃ Au/ Mo/ Ni/ WoO₃ WoO₃ WoO₃ MnOAu/ Mo/ Ni/ MnO MnO MnO Mn/Mg/O Au/ Mo/ Ni/ Mn/Mg/O Mn/Mg/O Mn/Mg/OMn₃O₄ Au/ Mo/ Ni/ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₂O₃ Au/ Mo/ Ni/ Mn₂O₃ Mn₂O₃ Mn₂O₃MnO₂ Au/ Mo/ Ni/ MnO₂ MnO₂ MnO₂ Mn₂O₇ Au/ Mo/ Ni/ Mn₂O₇ Mn₂O₇ Mn₂O₇ ReO₂Au/ Mo/ Ni/ ReO₂ ReO₂ ReO₂ ReO₃ Au/ Mo/ Ni/ ReO₃ ReO₃ ReO₃ Re₂O₇ Au/ Mo/Ni/ Re₂O₇ Re₂O₇ Re₂O₇ Mg₃Mn₃—B₂O₁₀ Au/ Mo/ Ni/ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀Mg₃Mn₃—B₂O₁₀ Mg₃(BO₃)₂ Au/ Mo/ Ni/ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂ NaWO₄Au/ Mo/ Ni/ NaWO₄ NaWO₄ NaWO₄ Mg₆MnO₈ Au/ Mo/ Ni/ Mg₆MnO₈ Mg₆MnO₈Mg₆MnO₈ Mn₂O₄ Au/ Mo/ Ni/ Mn₂O₄ Mn₂O₄ Mn₂O₄ (Li,Mg)₆—MnO₈ Au/ Mo/ Ni/(Li,Mg)₆—MnO₈ (Li,Mg)₆—MnO₈ Na₄P₂O₇ Au/ Mo/ Ni/ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇Mo₂O₈ Au/ Mo/ Ni/ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mn₃O₄/WO₄ Au/ Mo/ Ni/ Mn₃O₄/WO₄Mn₃O₄/WO₄ Mn₃O₄/WO₄ Na₂WO₄ Au/ Mo/ Ni/ Na₂WO₄ Na₂WO₄ Na₂WO₄ Zr₂Mo₂O₈ Au/Mo/ Ni/ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ NaMnO₄—/ Au/ Mo/ Ni/ MgO NaMnO₄—/NaMnO₄—/ NaMnO₄—/ MgO MgO MgO Na₁₀Mn—W₅O₁₇ Au/ Mo/ Ni/ Na₁₀Mn—W₅O₁₇Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ La₃NdO₆ Au/ Mo/ Ni/ La₃NdO₆ La₃NdO₆ La₃NdO₆LaNd₃O₆ Au/ Mo/ Ni/ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆ La_(1,5)Nd_(2,5)O₆ Au/ Mo/Ni/ La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆La_(2,5)Nd_(1,5)O₆ Au/ Mo/ Ni/ La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆La_(2,5)Nd_(1,5)O₆ La_(3,2)Nd_(0,8)O₆ Au/ Mo/ Ni/ La_(3,2)Nd_(0,8)O₆La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆ La_(3,5)Nd_(0,5)O₆ Au/ Mo/ Ni/La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆La_(3,8)Nd_(0,2)O₆ Au/ Mo/ Ni/ La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆La_(3,8)Nd_(0,2)O₆ Y—La Au/ Mo/ Ni/ Y—La Y—La Y—La Zr—La Au/ Mo/ Ni/Zr—La Zr—La Zr—La Pr—La Au/ Mo/ Ni/ Pr—La Pr—La Pr—La Ce—La Au/ Mo/ Ni/Ce—La Ce—La Ce—La

TABLE 7 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS (DOP) Dop NW Co Sb WV Li₂O Co/ Sb/ W/ V/ Li₂O Li₂O Li₂O Li₂O Na₂O Co/ Sb/ W/ V/ Na₂O Na₂ONa₂O Na₂O K₂O Co/ Sb/ W/ V/ K₂O K₂O K₂O K₂O Rb₂O Co/ Sb/ W/ V/ Rb₂O Rb₂ORb₂O Rb₂O Cs₂O Co/ Sb/ W/ V/ Cs₂O Cs₂O Cs₂O Cs₂O BeO Co/ Sb/ W/ V/ BeOBeO BeO BeO MgO Co/ Sb/ W/ V/ MgO MgO MgO MgO CaO Co/ Sb/ W/ V/ CaO CaOCaO CaO SrO Co/ Sb/ W/ V/ SrO SrO SrO SrO BaO Co/ Sb/ W/ V/ BaO BaO BaOBaO Sc₂O₃ Co/ Sb/ W/ V/ Sc₂O₃ Sc₂O₃ Sc₂O₃ Sc₂O₃ Y₂O₃ Co/ Sb/ W/ V/ Y₂O₃Y₂O₃ Y₂O₃ Y₂O₃ La₂O₃ Co/ Sb/ W/ V/ La₂O₃ La₂O₃ La₂O₃ La₂O₃ CeO₂ Co/ Sb/W/ V/ CeO₂ CeO₂ CeO₂ CeO₂ Ce₂O₃ Co/ Sb/ W/ V/ Ce₂O₃ Ce₂O₃ Ce₂O₃ Ce₂O₃Pr₂O₃ Co/ Sb/ W/ V/ Pr₂O₃ Pr₂O₃ Pr₂O₃ Pr₂O₃ Nd₂O₃ Co/ Sb/ W/ V/ Nd₂O₃Nd₂O₃ Nd₂O₃ Nd₂O₃ Sm₂O₃ Co/ Sb/ W/ V/ Sm₂O₃ Sm₂O₃ Sm₂O₃ Sm₂O₃ Eu₂O₃ Co/Sb/ W/ V/ Eu₂O₃ Eu₂O₃ Eu₂O₃ Eu₂O₃ Gd₂O₃ Co/ Sb/ W/ V/ Gd₂O₃ Gd₂O₃ Gd₂O₃Gd₂O₃ Tb₂O₃ Co/ Sb/ W/ V/ Tb₂O₃ Tb₂O₃ Tb₂O₃ Tb₂O₃ TbO₂ Co/ Sb/ W/ V/TbO₂ TbO₂ TbO₂ TbO₂ Tb₆O₁₁ Co/ Sb/ W/ V/ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁Dy₂O₃ Co/ Sb/ W/ V/ Dy₂O₃ Dy₂O₃ Dy₂O₃ Dy₂O₃ Ho₂O₃ Co/ Sb/ W/ V/ Ho₂O₃Ho₂O₃ Ho₂O₃ Ho₂O₃ Er₂O₃ Co/ Sb/ W/ V/ Er₂O₃ Er₂O₃ Er₂O₃ Er₂O₃ Tm₂O₃ Co/Sb/ W/ V/ Tm₂O₃ Tm₂O₃ Tm₂O₃ Tm₂O₃ Yb₂O₃ Co/ Sb/ W/ V/ Yb₂O₃ Yb₂O₃ Yb₂O₃Yb₂O₃ Lu₂O₃ Co/ Sb/ W/ V/ Lu₂O₃ Lu₂O₃ Lu₂O₃ Lu₂O₃ Ac₂O₃ Co/ Sb/ W/ V/Ac₂O₃ Ac₂O₃ Ac₂O₃ Ac₂O₃ Th₂O₃ Co/ Sb/ W/ V/ Th₂O₃ Th₂O₃ Th₂O₃ Th₂O₃ ThO₂Co/ Sb/ W/ V/ ThO₂ ThO₂ ThO₂ ThO₂ Pa₂O₃ Co/ Sb/ W/ V/ Pa₂O₃ Pa₂O₃ Pa₂O₃Pa₂O₃ PaO₂ Co/ Sb/ W/ V/ PaO₂ PaO₂ PaO₂ PaO₂ TiO₂ Co/ Sb/ W/ V/ TiO₂TiO₂ TiO₂ TiO₂ TiO Co/ Sb/ W/ V/ TiO TiO TiO TiO Ti₂O₃ Co/ Sb/ W/ V/Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₃O Co/ Sb/ W/ V/ Ti₃O Ti₃O Ti₃O Ti₃O Ti₂O Co/Sb/ W/ V/ Ti₂O Ti₂O Ti₂O Ti₂O Ti₃O₅ Co/ Sb/ W/ V/ Ti₃O₅ Ti₃O₅ Ti₃O₅Ti₃O₅ Ti₄O₇ Co/ Sb/ W/ V/ Ti₄O₇ Ti₄O₇ Ti₄O₇ Ti₄O₇ ZrO₂ Co/ Sb/ W/ V/ZrO₂ ZrO₂ ZrO₂ ZrO₂ HfO₂ Co/ Sb/ W/ V/ HfO₂ HfO₂ HfO₂ HfO₂ VO Co/ Sb/ W/V/ VO VO VO VO V₂O₃ Co/ Sb/ W/ V/ V₂O₃ V₂O₃ V₂O₃ V₂O₃ VO₂ Co/ Sb/ W/ V/VO₂ VO₂ VO₂ VO₂ V₂O₅ Co/ Sb/ W/ V/ V₂O₅ V₂O₅ V₂O₅ V₂O₅ V₃O₇ Co/ Sb/ W/V/ V₃O₇ V₃O₇ V₃O₇ V₃O₇ V₄O₉ Co/ Sb/ W/ V/ V₄O₉ V₄O₉ V₄O₉ V₄O₉ V₆O₁₃ Co/Sb/ W/ V/ V₆O₁₃ V₆O₁₃ V₆O₁₃ V₆O₁₃ NbO Co/ Sb/ W/ V/ NbO NbO NbO NbO NbO₂Co/ Sb/ W/ V/ NbO₂ NbO₂ NbO₂ NbO₂ Nb₂O₅ Co/ Sb/ W/ V/ Nb₂O₅ Nb₂O₅ Nb₂O₅Nb₂O₅ Nb₈O₁₉ Co/ Sb/ W/ V/ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₁₆O₃₈ Co/ Sb/W/ V/ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₂O₂₉ Co/ Sb/ W/ V/ Nb₁₂O₂₉Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₄₇O₁₁₆ Co/ Sb/ W/ V/ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Ta₂O₅ Co/ Sb/ W/ V/ Ta₂O₅ Ta₂O₅ Ta₂O₅ Ta₂O₅ CrO Co/Sb/ W/ V/ CrO CrO CrO CrO Cr₂O₃ Co/ Sb/ W/ V/ Cr₂O₃ Cr₂O₃ Cr₂O₃ Cr₂O₃CrO₂ Co/ Sb/ W/ V/ CrO₂ CrO₂ CrO₂ CrO₂ CrO₃ Co/ Sb/ W/ V/ CrO₃ CrO₃ CrO₃CrO₃ Cr₈O₂₁ Co/ Sb/ W/ V/ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ MoO₂ Co/ Sb/ W/ V/MoO₂ MoO₂ MoO₂ MoO₂ MoO₃ Co/ Sb/ W/ V/ MoO₃ MoO₃ MoO₃ MoO₃ W₂O₃ Co/ Sb/W/ V/ W₂O₃ W₂O₃ W₂O₃ W₂O₃ WoO₂ Co/ Sb/ W/ V/ WoO₂ WoO₂ WoO₂ WoO₂ WoO₃Co/ Sb/ W/ V/ WoO₃ WoO₃ WoO₃ WoO₃ MnO Co/ Sb/ W/ V/ MnO MnO MnO MnOMn/Mg/O Co/ Sb/ W/ V/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn₃O₄ Co/ Sb/ W/V/ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₂O₃ Co/ Sb/ W/ V/ Mn₂O₃ Mn₂O₃ Mn₂O₃ Mn₂O₃MnO₂ Co/ Sb/ W/ V/ MnO₂ MnO₂ MnO₂ MnO₂ Mn₂O₇ Co/ Sb/ W/ V/ Mn₂O₇ Mn₂O₇Mn₂O₇ Mn₂O₇ ReO₂ Co/ Sb/ W/ V/ ReO₂ ReO₂ ReO₂ ReO₂ ReO₃ Co/ Sb/ W/ V/ReO₃ ReO₃ ReO₃ ReO₃ Re₂O₇ Co/ Sb/ W/ V/ Re₂O₇ Re₂O₇ Re₂O₇ Re₂O₇Mg₃Mn₃—B₂O₁₀ Co/ Sb/ W/ V/ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀Mg₃Mn₃—B₂O₁₀ Mg₃(BO₃)₂ Co/ Sb/ W/ V/ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂Mg₃(BO₃)₂ NaWO₄ Co/ Sb/ W/ V/ NaWO₄ NaWO₄ NaWO₄ NaWO₄ Mg₆MnO₈ Co/ Sb/ W/V/ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mn₂O₄ Co/ Sb/ W/ V/ Mn₂O₄ Mn₂O₄ Mn₂O₄Mn₂O₄ (Li,Mg)₆—MnO₈ Co/ Sb/ W/ V/ (Li,Mg)₆—MnO₈ (Li,Mg)₆—MnO₈(Li,Mg)₆—MnO₈ (Li,Mg)₆—MnO₈ Na₄P₂O₇ Co/ Sb/ W/ V/ Na₄P₂O₇ Na₄P₂O₇Na₄P₂O₇ Na₄P₂O₇ Mo₂O₈ Co/ Sb/ W/ V/ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mn₃O₄/WO₄Co/ Sb/ W/ V/ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Na₂WO₄ Co/ Sb/ W/V/ Na₂WO₄ Na₂WO₄ Na₂WO₄ Na₂WO₄ Zr₂Mo₂O₈ Co/ Sb/ W/ V/ Zr₂Mo₂O₈ Zr₂Mo₂O₈Zr₂Mo₂O₈ Zr₂Mo₂O₈ NaMnO₄—/ Co/ Sb/ W/ V/ MgO NaMnO₄—/ NaMnO₄—/ NaMnO₄—/NaMnO₄—/ MgO MgO MgO MgO Na₁₀Mn—W₅O₁₇ Co/ Sb/ W/ V/ Na₁₀Mn—W₅O₁₇Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ La₃NdO₆ Co/ Sb/ W/ V/ La₃NdO₆La₃NdO₆ La₃NdO₆ La₃NdO₆ LaNd₃O₆ Co/ Sb/ W/ V/ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆LaNd₃O₆ La_(1,5)Nd_(2,5)O₆ Co/ Sb/ W/ V/ La_(1,5)Nd_(2,5)O₆La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆La_(2,5)Nd_(1,5)O₆ Co/ Sb/ W/ V/ La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆ La_(3,2)Nd_(0,8)O₆ Co/ Sb/ W/ V/La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆La_(3,2)Nd_(0,8)O₆ La_(3,5)Nd_(0,5)O₆ Co/ Sb/ W/ V/ La_(3,5)Nd_(0,5)O₆La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆La_(3,8)Nd_(0,2)O₆ Co/ Sb/ W/ V/ La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆ Y—La Co/ Sb/ W/ V/ Y—La Y—La Y—LaY—La Zr—La Co/ Sb/ W/ V/ Zr—La Zr—La Zr—La Zr—La Pr—La Co/ Sb/ W/ V/Pr—La Pr—La Pr—La Pr—La Ce—La Co/ Sb/ W/ V/ Ce—La Ce—La Ce—La Ce—La DopNW Ag Te Pd Ir Li₂O Ag/ Te/ Pd/ Ir/ Li₂O Li₂O Li₂O Li₂O Na₂O Ag/ Te/ Pd/Ir/ Na₂O Na₂O Na₂O Na₂O K₂O Ag/ Te/ Pd/ Ir/ K₂O K₂O K₂O K₂O Rb₂O Ag/ Te/Pd/ Ir/ Rb₂O Rb₂O Rb₂O Rb₂O Cs₂O Ag/ Te/ Pd/ Ir/ Cs₂O Cs₂O Cs₂O Cs₂O BeOAg/ Te/ Pd/ Ir/ BeO BeO BeO BeO MgO Ag/ Te/ Pd/ Ir/ MgO MgO MgO MgO CaOAg/ Te/ Pd/ Ir/ CaO CaO CaO CaO SrO Ag/ Te/ Pd/ Ir/ SrO SrO SrO SrO BaOAg/ Te/ Pd/ Ir/ BaO BaO BaO BaO Sc₂O₃ Ag/ Te/ Pd/ Ir/ Sc₂O₃ Sc₂O₃ Sc₂O₃Sc₂O₃ Y₂O₃ Ag/ Te/ Pd/ Ir/ Y₂O₃ Y₂O₃ Y₂O₃ Y₂O₃ La₂O₃ Ag/ Te/ Pd/ Ir/La₂O₃ La₂O₃ La₂O₃ La₂O₃ CeO₂ Ag/ Te/ Pd/ Ir/ CeO₂ CeO₂ CeO₂ CeO₂ Ce₂O₃Ag/ Te/ Pd/ Ir/ Ce₂O₃ Ce₂O₃ Ce₂O₃ Ce₂O₃ Pr₂O₃ Ag/ Te/ Pd/ Ir/ Pr₂O₃Pr₂O₃ Pr₂O₃ Pr₂O₃ Nd₂O₃ Ag/ Te/ Pd/ Ir/ Nd₂O₃ Nd₂O₃ Nd₂O₃ Nd₂O₃ Sm₂O₃Ag/ Te/ Pd/ Ir/ Sm₂O₃ Sm₂O₃ Sm₂O₃ Sm₂O₃ Eu₂O₃ Ag/ Te/ Pd/ Ir/ Eu₂O₃Eu₂O₃ Eu₂O₃ Eu₂O₃ Gd₂O₃ Ag/ Te/ Pd/ Ir/ Gd₂O₃ Gd₂O₃ Gd₂O₃ Gd₂O₃ Tb₂O₃Ag/ Te/ Pd/ Ir/ Tb₂O₃ Tb₂O₃ Tb₂O₃ Tb₂O₃ TbO₂ Ag/ Te/ Pd/ Ir/ TbO₂ TbO₂TbO₂ TbO₂ Tb₆O₁₁ Ag/ Te/ Pd/ Ir/ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Dy₂O₃ Ag/Te/ Pd/ Ir/ Dy₂O₃ Dy₂O₃ Dy₂O₃ Dy₂O₃ Ho₂O₃ Ag/ Te/ Pd/ Ir/ Ho₂O₃ Ho₂O₃Ho₂O₃ Ho₂O₃ Er₂O₃ Ag/ Te/ Pd/ Ir/ Er₂O₃ Er₂O₃ Er₂O₃ Er₂O₃ Tm₂O₃ Ag/ Te/Pd/ Ir/ Tm₂O₃ Tm₂O₃ Tm₂O₃ Tm₂O₃ Yb₂O₃ Ag/ Te/ Pd/ Ir/ Yb₂O₃ Yb₂O₃ Yb₂O₃Yb₂O₃ Lu₂O₃ Ag/ Te/ Pd/ Ir/ Lu₂O₃ Lu₂O₃ Lu₂O₃ Lu₂O₃ Ac₂O₃ Ag/ Te/ Pd/Ir/ Ac₂O₃ Ac₂O₃ Ac₂O₃ Ac₂O₃ Th₂O₃ Ag/ Te/ Pd/ Ir/ Th₂O₃ Th₂O₃ Th₂O₃Th₂O₃ ThO₂ Ag/ Te/ Pd/ Ir/ ThO₂ ThO₂ ThO₂ ThO₂ Pa₂O₃ Ag/ Te/ Pd/ Ir/Pa₂O₃ Pa₂O₃ Pa₂O₃ Pa₂O₃ PaO₂ Ag/ Te/ Pd/ Ir/ PaO₂ PaO₂ PaO₂ PaO₂ TiO₂Ag/ Te/ Pd/ Ir/ TiO₂ TiO₂ TiO₂ TiO₂ TiO Ag/ Te/ Pd/ Ir/ TiO TiO TiO TiOTi₂O₃ Ag/ Te/ Pd/ Ir/ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₃O Ag/ Te/ Pd/ Ir/ Ti₃OTi₃O Ti₃O Ti₃O Ti₂O Ag/ Te/ Pd/ Ir/ Ti₂O Ti₂O Ti₂O Ti₂O Ti₃O₅ Ag/ Te/Pd/ Ir/ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₄O₇ Ag/ Te/ Pd/ Ir/ Ti₄O₇ Ti₄O₇ Ti₄O₇Ti₄O₇ ZrO₂ Ag/ Te/ Pd/ Ir/ ZrO₂ ZrO₂ ZrO₂ ZrO₂ HfO₂ Ag/ Te/ Pd/ Ir/ HfO₂HfO₂ HfO₂ HfO₂ VO Ag/ Te/ Pd/ Ir/ VO VO VO VO V₂O₃ Ag/ Te/ Pd/ Ir/ V₂O₃V₂O₃ V₂O₃ V₂O₃ VO₂ Ag/ Te/ Pd/ Ir/ VO₂ VO₂ VO₂ VO₂ V₂O₅ Ag/ Te/ Pd/ Ir/V₂O₅ V₂O₅ V₂O₅ V₂O₅ V₃O₇ Ag/ Te/ Pd/ Ir/ V₃O₇ V₃O₇ V₃O₇ V₃O₇ V₄O₉ Ag/Te/ Pd/ Ir/ V₄O₉ V₄O₉ V₄O₉ V₄O₉ V₆O₁₃ Ag/ Te/ Pd/ Ir/ V₆O₁₃ V₆O₁₃ V₆O₁₃V₆O₁₃ NbO Ag/ Te/ Pd/ Ir/ NbO NbO NbO NbO NbO₂ Ag/ Te/ Pd/ Ir/ NbO₂ NbO₂NbO₂ NbO₂ Nb₂O₅ Ag/ Te/ Pd/ Ir/ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₈O₁₉ Ag/ Te/Pd/ Ir/ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₁₆O₃₈ Ag/ Te/ Pd/ Ir/ Nb₁₆O₃₈Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₂O₂₉ Ag/ Te/ Pd/ Ir/ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉Nb₁₂O₂₉ Nb₄₇O₁₁₆ Ag/ Te/ Pd/ Ir/ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆Ta₂O₅ Ag/ Te/ Pd/ Ir/ Ta₂O₅ Ta₂O₅ Ta₂O₅ Ta₂O₅ CrO Ag/ Te/ Pd/ Ir/ CrOCrO CrO CrO Cr₂O₃ Ag/ Te/ Pd/ Ir/ Cr₂O₃ Cr₂O₃ Cr₂O₃ Cr₂O₃ CrO₂ Ag/ Te/Pd/ Ir/ CrO₂ CrO₂ CrO₂ CrO₂ CrO₃ Ag/ Te/ Pd/ Ir/ CrO₃ CrO₃ CrO₃ CrO₃Cr₈O₂₁ Ag/ Te/ Pd/ Ir/ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ MoO₂ Ag/ Te/ Pd/ Ir/MoO₂ MoO₂ MoO₂ MoO₂ MoO₃ Ag/ Te/ Pd/ Ir/ MoO₃ MoO₃ MoO₃ MoO₃ W₂O₃ Ag/Te/ Pd/ Ir/ W₂O₃ W₂O₃ W₂O₃ W₂O₃ WoO₂ Ag/ Te/ Pd/ Ir/ WoO₂ WoO₂ WoO₂ WoO₂WoO₃ Ag/ Te/ Pd/ Ir/ WoO₃ WoO₃ WoO₃ WoO₃ MnO Ag/ Te/ Pd/ Ir/ MnO MnO MnOMnO Mn/Mg/O Ag/ Te/ Pd/ Ir/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn₃O₄ Ag/Te/ Pd/ Ir/ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₂O₃ Ag/ Te/ Pd/ Ir/ Mn₂O₃ Mn₂O₃Mn₂O₃ Mn₂O₃ MnO₂ Ag/ Te/ Pd/ Ir/ MnO₂ MnO₂ MnO₂ MnO₂ Mn₂O₇ Ag/ Te/ Pd/Ir/ Mn₂O₇ Mn₂O₇ Mn₂O₇ Mn₂O₇ ReO₂ Ag/ Te/ Pd/ Ir/ ReO₂ ReO₂ ReO₂ ReO₂ReO₃ Ag/ Te/ Pd/ Ir/ ReO₃ ReO₃ ReO₃ ReO₃ Re₂O₇ Ag/ Te/ Pd/ Ir/ Re₂O₇Re₂O₇ Re₂O₇ Re₂O₇ Mg₃Mn₃—B₂O₁₀ Ag/ Te/ Pd/ Ir/ Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀ Mg₃(BO₃)₂ Ag/ Te/ Pd/ Ir/ Mg₃(BO₃)₂ Mg₃(BO₃)₂Mg₃(BO₃)₂ Mg₃(BO₃)₂ NaWO₄ Ag/ Te/ Pd/ Ir/ NaWO₄ NaWO₄ NaWO₄ NaWO₄Mg₆MnO₈ Ag/ Te/ Pd/ Ir/ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mn₂O₄ Ag/ Te/Pd/ Ir/ Mn₂O₄ Mn₂O₄ Mn₂O₄ Mn₂O₄ (Li,Mg)₆—MnO₈ Ag/ Te/ Pd/ Ir/(Li,Mg)₆—MnO₈ (Li,Mg)₆—MnO₈ (Li,Mg)₆—MnO₈ (Li,Mg)₆—MnO₈ Na₄P₂O₇ Ag/ Te/Pd/ Ir/ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Mo₂O₈ Ag/ Te/ Pd/ Ir/ Mo₂O₈Mo₂O₈ Mo₂O₈ Mo₂O₈ Mn₃O₄/WO₄ Ag/ Te/ Pd/ Ir/ Mn₃O₄/WO₄ Mn₃O₄/WO₄Mn₃O₄/WO₄ Mn₃O₄/WO₄ Na₂WO₄ Ag/ Te/ Pd/ Ir/ Na₂WO₄ Na₂WO₄ Na₂WO₄ Na₂WO₄Zr₂Mo₂O₈ Ag/ Te/ Pd/ Ir/ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ NaMnO₄—/Ag/ Te/ Pd/ Ir/ MgO NaMnO₄—/ NaMnO₄—/ NaMnO₄—/ NaMnO₄—/ MgO MgO MgO MgONa₁₀Mn—W₅O₁₇ Ag/ Te/ Pd/ Ir/ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇Na₁₀Mn—W₅O₁₇ La₃NdO₆ Ag/ Te/ Pd/ Ir/ La₃NdO₆ La₃NdO₆ La₃NdO₆ La₃NdO₆LaNd₃O₆ Ag/ Te/ Pd/ Ir/ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆La_(1,5)Nd_(2,5)O₆ Ag/ Te/ Pd/ Ir/ La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆La_(1,5)Nd_(2,5)O₆ La_(1,5)Nd_(2,5)O₆ La_(2,5)Nd_(1,5)O₆ Ag/ Te/ Pd/ Ir/La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆ La_(2,5)Nd_(1,5)O₆La_(2,5)Nd_(1,5)O₆ La_(3,2)Nd_(0,8)O₆ Ag/ Te/ Pd/ Ir/ La_(3,2)Nd_(0,8)O₆La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆ La_(3,2)Nd_(0,8)O₆La_(3,5)Nd_(0,5)O₆ Ag/ Te/ Pd/ Ir/ La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆La_(3,5)Nd_(0,5)O₆ La_(3,5)Nd_(0,5)O₆ La_(3,8)Nd_(0,2)O₆ Ag/ Te/ Pd/ Ir/La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆ La_(3,8)Nd_(0,2)O₆La_(3,8)Nd_(0,2)O₆ Y—La Ag/ Te/ Pd/ Ir/ Y—La Y—La Y—La Y—La Zr—La Ag/Te/ Pd/ Ir/ Zr—La Zr—La Zr—La Zr—La Pr—La Ag/ Te/ Pd/ Ir/ Pr—La Pr—LaPr—La Pr—La Ce—La Ag/ Te/ Pd/ Ir/ Ce—La Ce—La Ce—La Ce—La

TABLE 8 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS (DOP) Dop NW Mn TiLi₂O Mn/ Ti/ Li₂O Li₂O Na₂O Mn/ Ti/ Na₂O Na₂O K₂O Mn/ Ti/ K₂O K₂O Rb₂OMn/ Ti/ Rb₂O Rb₂O Cs₂O Mn/ Ti/ Cs₂O Cs₂O BeO Mn/ Ti/ BeO BeO MgO Mn/ Ti/MgO MgO CaO Mn/ Ti/ CaO CaO SrO Mn/ Ti/ SrO SrO BaO Mn/ Ti/ BaO BaOSc₂O₃ Mn/ Ti/ Sc₂O₃ Sc₂O₃ Y₂O₃ Mn/ Ti/ Y₂O₃ Y₂O₃ La₂O₃ Mn/ Ti/ La₂O₃La₂O₃ CeO₂ Mn/ Ti/ CeO₂ CeO₂ Ce₂O₃ Mn/ Ti/ Ce₂O₃ Ce₂O₃ Pr₂O₃ Mn/ Ti/Pr₂O₃ Pr₂O₃ Nd₂O₃ Mn/ Ti/ Nd₂O₃ Nd₂O₃ Sm₂O₃ Mn/ Ti/ Sm₂O₃ Sm₂O₃ Eu₂O₃Mn/ Ti/ Eu₂O₃ Eu₂O₃ Gd₂O₃ Mn/ Ti/ Gd₂O₃ Gd₂O₃ Tb₂O₃ Mn/ Ti/ Tb₂O₃ Tb₂O₃TbO₂ Mn/ Ti/ TbO₂ TbO₂ Tb₆O₁₁ Mn/ Ti/ Tb₆O₁₁ Tb₆O₁₁ Dy₂O₃ Mn/ Ti/ Dy₂O₃Dy₂O₃ Ho₂O₃ Mn/ Ti/ Ho₂O₃ Ho₂O₃ Er₂O₃ Mn/ Ti/ Er₂O₃ Er₂O₃ Tm₂O₃ Mn/ Ti/Tm₂O₃ Tm₂O₃ Yb₂O₃ Mn/ Ti/ Yb₂O₃ Yb₂O₃ Lu₂O₃ Mn/ Ti/ Lu₂O₃ Lu₂O₃ Ac₂O₃Mn/ Ti/ Ac₂O₃ Ac₂O₃ Th₂O₃ Mn/ Ti/ Th₂O₃ Th₂O₃ ThO₂ Mn/ Ti/ ThO₂ ThO₂Pa₂O₃ Mn/ Ti/ Pa₂O₃ Pa₂O₃ PaO₂ Mn/ Ti/ PaO₂ PaO₂ TiO₂ Mn/ Ti/ TiO₂ TiO₂TiO Mn/ Ti/ TiO TiO Ti₂O₃ Mn/ Ti/ Ti₂O₃ Ti₂O₃ Ti₃O Mn/ Ti/ Ti₃O Ti₃OTi₂O Mn/ Ti/ Ti₂O Ti₂O Ti₃O₅ Mn/ Ti/ Ti₃O₅ Ti₃O₅ Ti₄O₇ Mn/ Ti/ Ti₄O₇Ti₄O₇ ZrO₂ Mn/ Ti/ ZrO₂ ZrO₂ HfO₂ Mn/ Ti/ HfO₂ HfO₂ VO Mn/ Ti/ VO VOV₂O₃ Mn/ Ti/ V₂O₃ V₂O₃ VO₂ Mn/ Ti/ VO₂ VO₂ V₂O₅ Mn/ Ti/ V₂O₅ V₂O₅ V₃O₇Mn/ Ti/ V₃O₇ V₃O₇ V₄O₉ Mn/ Ti/ V₄O₉ V₄O₉ V₆O₁₃ Mn/ Ti/ V₆O₁₃ V₆O₁₃ NbOMn/ Ti/ NbO NbO NbO₂ Mn/ Ti/ NbO₂ NbO₂ Nb₂O₅ Mn/ Ti/ Nb₂O₅ Nb₂O₅ Nb₈O₁₉Mn/ Ti/ Nb₈O₁₉ Nb₈O₁₉ Nb₁₆O₃₈ Mn/ Ti/ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₂O₂₉ Mn/ Ti/Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₄₇O₁₁₆ Mn/ Ti/ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Ta₂O₅ Mn/ Ti/ Ta₂O₅Ta₂O₅ CrO Mn/ Ti/ CrO CrO Cr₂O₃ Mn/ Ti/ Cr₂O₃ Cr₂O₃ CrO₂ Mn/ Ti/ CrO₂CrO₂ CrO₃ Mn/ Ti/ CrO₃ CrO₃ Cr₈O₂₁ Mn/ Ti/ Cr₈O₂₁ Cr₈O₂₁ MoO₂ Mn/ Ti/MoO₂ MoO₂ MoO₃ Mn/ Ti/ MoO₃ MoO₃ W₂O₃ Mn/ Ti/ W₂O₃ W₂O₃ WoO₂ Mn/ Ti/WoO₂ WoO₂ WoO₃ Mn/ Ti/ WoO₃ WoO₃ MnO Mn/ Ti/ MnO MnO Mn/Mg/O Mn/ Ti/Mn/Mg/O Mn/Mg/O Mn₃O₄ Mn/ Ti/ Mn₃O₄ Mn₃O₄ Mn₂O₃ Mn/ Ti/ Mn₂O₃ Mn₂O₃ MnO₂Mn/ Ti/ MnO₂ MnO₂ Mn₂O₇ Mn/ Ti/ Mn₂O₇ Mn₂O₇ ReO₂ Mn/ Ti/ ReO₂ ReO₂ ReO₃Mn/ Ti/ ReO₃ ReO₃ Re₂O₇ Mn/ Ti/ Re₂O₇ Re₂O₇ Mg₃Mn₃—B₂O₁₀ Mn/ Ti/Mg₃Mn₃—B₂O₁₀ Mg₃Mn₃—B₂O₁₀ Mg₃(BO₃)₂ Mn/ Ti/ Mg₃(BO₃)₂ Mg₃(BO₃)₂ NaWO₄Mn/ Ti/ NaWO₄ NaWO₄ Mg₆MnO₈ Mn/ Ti/ Mg₆MnO₈ Mg₆MnO₈ Mn₂O₄ Mn/ Ti/ Mn₂O₄Mn₂O₄ (Li,Mg)₆—MnO₈ Mn/ Mn/ (Li,Mg)₆—MnO₈ (Li,Mg)₆—MnO₈ Na₄P₂O₇ Mn/ Ti/Na₄P₂O₇ Na₄P₂O₇ Mo₂O₈ Mn/ Ti/ Mo₂O₈ Mo₂O₈ Mn₃O₄/WO₄ Mn/ Ti/ Mn₃O₄/WO₄Mn₃O₄/WO₄ Na₂WO₄ Mn/ Ti/ Na₂WO₄ Na₂WO₄ Zr₂Mo₂O₈ Mn/ Ti/ Zr₂Mo₂O₈Zr₂Mo₂O₈ NaMnO₄—/ Mn/ Ti/ MgO NaMnO₄—/ NaMnO₄—/ MgO MgO Na₁₀Mn—W₅O₁₇ Mn/Ti/ Na₁₀Mn—W₅O₁₇ Na₁₀Mn—W₅O₁₇ La₃NdO₆ Mn/ Ti/ La₃NdO₆ La₃NdO₆ LaNd₃O₆Mn/ Ti/ LaNd₃O₆ LaNd₃O₆ La_(1,5)Nd_(2,5)O₆ Mn/ Ti/ La_(1,5)Nd_(2,5)O₆La_(1,5)Nd_(2,5)O₆ La_(2,5)Nd_(1,5)O₆ Mn/ Ti/ La_(2,5)Nd_(1,5)O₆La_(2,5)Nd_(1,5)O₆ La_(3,2)Nd_(0,8)O₆ Mn/ Ti/ La_(3,2)Nd_(0,8)O₆La_(3,2)Nd_(0,8)O₆ La_(3,5)Nd_(0,5)O₆ Mn/ Ti/ La_(3,5)Nd_(0,5)O₆La_(3,5)Nd_(0,5)O₆ La_(3,8)Nd_(0,2)O₆ Mn/ Ti/ La_(3,8)Nd_(0,2)O₆La_(3,8)Nd_(0,2)O₆ Y—La Mn/ Ti/ Y—La Y—La Zr—La Mn/ Ti/ Zr—La Zr—LaPr—La Mn/ Ti/ Pr—La Pr—La Ce—La Mn/ Ti/ Ce—La Ce—La

TABLE 9 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS (DOP) NW Dop La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Eu/Na Eu/Na/ Eu/Na/ Eu/Na/ Eu/Na/ Eu/Na/Eu/Na/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Na Sr/Na/ Sr/Na/ Sr/Na/Sr/Na/ Sr/Na/ Sr/Na/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/Zr/Eu/CaNa/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/Na/Zr/Eu/Ca/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Mg/Na Mg/Na/ Mg/Na/Mg/Na/ Mg/Na/ Mg/Na/ Mg/Na/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Sr/Sm/Ho/Tm Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/WSr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Sr/Zr Sr/Zr/ Sr/Zr/ Sr/Zr/ Sr/Zr/ Sr/Zr/ Sr/Zr/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ Rb/Sr/ Mg/La/K Mg/La/K/ Mg/La/K/ Mg/La/K/ Mg/La/K/Mg/La/K/ Mg/La/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/K/Mg/TmNa/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/Dy/K Na/Dy/K/ Na/Dy/K/ Na/Dy/K/Na/Dy/K/ Na/Dy/K/ Na/Dy/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Na/La/Dy Na/La/Dy/ Na/La/Dy/ Na/La/Dy/ Na/La/Dy/ Na/La/Dy/ Na/La/Dy/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/La/Eu Na/La/Eu/ Na/La/Eu/Na/La/Eu/ Na/La/Eu/ Na/La/Eu/ Na/La/Eu/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Na/La/Eu/In Na/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/Na/La/Eu/In/ Na/La/Eu/In/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/CeSr/Ce/ Sr/Ce/ Sr/Ce/ Sr/Ce/ Sr/Ce/ Sr/Ce/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃Rb/Sr/ Na/La/K Na/La/K/ Na/La/K/ Na/La/K/ Na/La/K/ Na/La/K/ Na/La/K/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/La/Li/Cs Na/La/Li/Cs/Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ K/La K/La/ K/La/ K/La/ K/La/ K/La/ K/La/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ K/La/S K/La/S/ K/La/S/ K/La/S/K/La/S/ K/La/S/ K/La/S/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ K/Na K/Na/K/Na/ K/Na/ K/Na/ K/Na/ K/Na/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Li/Cs Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Li/Cs/La Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/Li/Cs/La/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/Cs/La/Tm Li/Cs/La/Tm/Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Tb Sr/Tb/ Sr/Tb/ Sr/Tb/ Sr/Tb/ Sr/Tb/Sr/Tb/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ Rb/Sr/ Li/Cs/Sr/Tm Li/Cs/Sr/Tm/Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/Sr/Cs Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Li/Sr/Zn/K Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/Li/Sr/Zn/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/Ga/Cs Li/Ga/Cs/Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/K/Sr/La Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Li/Na Li/Na/ Li/Na/ Li/Na/ Li/Na/ Li/Na/ Li/Na/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/Na/Rb/Ga Li/Na/Rb/Ga/ Li/Na/Rb/Ga/Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/Na/Sr Li/Na/Sr/ Li/Na/Sr/ Li/Na/Sr/ Li/Na/Sr/Li/Na/Sr/ Li/Na/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/Na/Sr/LaLi/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/Li/Na/Sr/La/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/Sm/Cs Li/Sm/Cs/Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Ba/Sm/Yb/S Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Sr/Ce/K Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ Rb/Sr/ Ba/Tm/K/La Ba/Tm/K/La/ Ba/Tm/K/La/Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Ba/Tm/Zn/K Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ La2O3 Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Cs/K/LaCs/K/La/ Cs/K/La/ Cs/K/La/ Cs/K/La/ Cs/K/La/ Cs/K/La/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Cs/La/Tm/Na Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Cs/Li/K/La Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/Cs/Li/K/La/ Cs/Li/K/La/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Sm/Li/Sr/Cs Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Cs/LaSr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Tm/Li/Cs Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Zn/K Zn/K/ Zn/K/ Zn/K/ Zn/K/ Zn/K/ Zn/K/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Zr/Cs/K/La Zr/Cs/K/La/ Zr/Cs/K/La/ Zr/Cs/K/La/Zr/Cs/K/La/ Zr/Cs/K/La/ Zr/Cs/K/La/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Rb/Ca/In/Ni Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ Rb/Ca/In/Ni/Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Ho/TmSr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ La/Nd/S La/Nd/S/ La/Nd/S/ La/Nd/S/ La/Nd/S/La/Nd/S/ La/Nd/S/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/Rb/CaLi/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/K Li/K/ Li/K/ Li/K/ Li/K/ Li/K/ Li/K/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Tm/Lu/Ta/P Tm/Lu/Ta/P/ Tm/Lu/Ta/P/Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Rb/Ca/Dy/P Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ Rb/Ca/Dy/P/Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Mg/La/Yb/Zn Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Mg/La/Yb/Zn/Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Zr/KSr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ Rb/Sr/ Rb/Sr/Lu Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/Rb/Sr/Lu/ Rb/Sr/Lu/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/Sr/Lu/NbNa/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/Na/Sr/Lu/Nb/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/Eu/Hf Na/Eu/Hf/Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Dy/Rb/Gd Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/Dy/Rb/Gd/ Dy/Rb/Gd/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/Pt/BiNa/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Rb/Hf Rb/Hf/ Rb/Hf/ Rb/Hf/ Rb/Hf/ Rb/Hf/Rb/Hf/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ca/Cs Ca/Cs/ Ca/Cs/ Ca/Cs/Ca/Cs/ Ca/Cs/ Ca/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ca/Mg/NaCa/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Hf/Bi Hf/Bi/ Hf/Bi/ Hf/Bi/ Hf/Bi/ Hf/Bi/Hf/Bi/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Sn Sr/Sn/ Sr/Sn/ Sr/Sn/Sr/Sn/ Sr/Sn/ Sr/Sn/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Pr/KSr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ Rb/Sr/ Sr/W Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Nb Sr/Nb/ Sr/Nb/ Sr/Nb/ Sr/Nb/ Sr/Nb/Sr/Nb/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Zr/W Zr/W/ Zr/W/ Zr/W/Zr/W/ Zr/W/ Zr/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Y/W Y/W/ Y/W/Y/W/ Y/W/ Y/W/ Y/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/W Na/W/Na/W/ Na/W/ Na/W/ Na/W/ Na/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Bi/WBi/W/ Bi/W/ Bi/W/ Bi/W/ Bi/W/ Bi/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Bi/Cs Bi/Cs/ Bi/Cs/ Bi/Cs/ Bi/Cs/ Bi/Cs/ Bi/Cs/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Bi/Ca Bi/Ca/ Bi/Ca/ Bi/Ca/ Bi/Ca/ Bi/Ca/Bi/Ca/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Bi/Sn Bi/Sn/ Bi/Sn/ Bi/Sn/Bi/Sn/ Bi/Sn/ Bi/Sn/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Bi/Sb Bi/Sb/Bi/Sb/ Bi/Sb/ Bi/Sb/ Bi/Sb/ Bi/Sb/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Ge/Hf Ge/Hf/ Ge/Hf/ Ge/Hf/ Ge/Hf/ Ge/Hf/ Ge/Hf/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Hf/Sm Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sb/Ag Sb/Ag/ Sb/Ag/ Sb/Ag/ Sb/Ag/ Sb/Ag/Sb/Ag/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sb/Bi Sb/Bi/ Sb/Bi/ Sb/Bi/Sb/Bi/ Sb/Bi/ Sb/Bi/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sb/Au Sb/Au/Sb/Au/ Sb/Au/ Sb/Au/ Sb/Au/ Sb/Au/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Sb/Sm Sb/Sm/ Sb/Sm/ Sb/Sm/ Sb/Sm/ Sb/Sm/ Sb/Sm/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Sr/Tb/K Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/Sr/Tb/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ Rb/Sr/ Sb/Sr Sb/Sr/ Sb/Sr/ Sb/Sr/Sb/Sr/ Sb/Sr/ Sb/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sb/W Sb/W/Sb/W/ Sb/W/ Sb/W/ Sb/W/ Sb/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Sb/Hf Sb/Hf/ Sb/Hf/ Sb/Hf/ Sb/Hf/ Sb/Hf/ Sb/Hf/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Sb/Yb Sb/Yb/ Sb/Yb/ Sb/Yb/ Sb/Yb/ Sb/Yb/ Sb/Yb/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sb/Sn Sb/Sn/ Sb/Sn/ Sb/Sn/ Sb/Sn/ Sb/Sn/Sb/Sn/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Yb/Au Yb/Au/ Yb/Au/ Yb/Au/Yb/Au/ Yb/Au/ Yb/Au/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Yb/Ta Yb/Ta/Yb/Ta/ Yb/Ta/ Yb/Ta/ Yb/Ta/ Yb/Ta/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Yb/W Yb/W/ Yb/W/ Yb/W/ Yb/W/ Yb/W/ Yb/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Yb/Sr Yb/Sr/ Yb/Sr/ Yb/Sr/ Yb/Sr/ Yb/Sr/ Yb/Sr/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Yb/Pb Yb/Pb/ Yb/Pb/ Yb/Pb/ Yb/Pb/ Yb/Pb/Yb/Pb/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Yb/W Yb/W/ Yb/W/ Yb/W/Yb/W/ Yb/W/ Yb/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Yb/Ag Yb/Ag/Yb/Ag/ Yb/Ag/ Yb/Ag/ Yb/Ag/ Yb/Ag/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Au/Sr Au/Sr/ Au/Sr/ Au/Sr/ Au/Sr/ Au/Sr/ Au/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Sr/Hf/K Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/Sr/Hf/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ Rb/Sr/ W/Ge W/Ge/ W/Ge/ W/Ge/W/Ge/ W/Ge/ W/Ge/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ta/Sr Ta/Sr/Ta/Sr/ Ta/Sr/ Ta/Sr/ Ta/Sr/ Ta/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Ta/Hf Ta/Hf/ Ta/Hf/ Ta/Hf/ Ta/Hf/ Ta/Hf/ Ta/Hf/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ W/Au W/Au/ W/Au/ W/Au/ W/Au/ W/Au/ W/Au/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Ca/W Ca/W/ Ca/W/ Ca/W/ Ca/W/ Ca/W/ Ca/W/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Au/Re Au/Re/ Au/Re/ Au/Re/ Au/Re/ Au/Re/Au/Re/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sm/Li Sm/Li/ Sm/Li/ Sm/Li/Sm/Li/ Sm/Li/ Sm/Li/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ La/K La/K/La/K/ La/K/ La/K/ La/K/ La/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Zn/Cs Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Na/K/Mg Na/K/Mg/ Na/K/Mg/ Na/K/Mg/ Na/K/Mg/ Na/K/Mg/Na/K/Mg/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Zr/Cs Zr/Cs/ Zr/Cs/Zr/Cs/ Zr/Cs/ Zr/Cs/ Zr/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ca/CeCa/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Na/Li/Cs Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/Na/Li/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/Sr Li/Sr/ Li/Sr/Li/Sr/ Li/Sr/ Li/Sr/ Li/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆La/Dy/K La/Dy/K/ La/Dy/K/ La/Dy/K/ La/Dy/K/ La/Dy/K/ La/Dy/K/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Pr Sr/Pr/ Sr/Pr/ Sr/Pr/ Sr/Pr/ Sr/Pr/Sr/Pr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ Rb/Sr/ Dy/K Dy/K/ Dy/K/ Dy/K/ Dy/K/Dy/K/ Dy/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ La/Mg La/Mg/ La/Mg/La/Mg/ La/Mg/ La/Mg/ La/Mg/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Na/Nd/In/K Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/Na/Nd/In/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ In/Sr In/Sr/ In/Sr/In/Sr/ In/Sr/ In/Sr/ In/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/CsSr/Cs/ Sr/Cs/ Sr/Cs/ Sr/Cs/ Sr/Cs/ Sr/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Rb/Ga/Tm/Cs Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ga/CsGa/Cs/ Ga/Cs/ Ga/Cs/ Ga/Cs/ Ga/Cs/ Ga/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ K/La/Zr/Ag K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/K/La/Zr/Ag/ K/La/Zr/Ag/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Lu/FeLu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Sr/Tm Sr/Tm/ Sr/Tm/ Sr/Tm/ Sr/Tm/ Sr/Tm/ Sr/Tm/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ La/Dy La/Dy/ La/Dy/ La/Dy/ La/Dy/ La/Dy/La/Dy/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sm/Li/Sr Sm/Li/Sr/Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Mg/K Mg/K/ Mg/K/ Mg/K/ Mg/K/ Mg/K/ Mg/K/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/Rb/Ga Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Li/Cs/Tm Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Zr/K Zr/K/ Zr/K/ Zr/K/ Zr/K/ Zr/K/Zr/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Hf/Rb Sr/Hf/Rb/ Sr/Hf/Rb/Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃Rb/Sr/ Li/Cs Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/K/La Li/K/La/ Li/K/La/ Li/K/La/ Li/K/La/ Li/K/La/Li/K/La/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ce/Zr/La Ce/Zr/La/Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Ca/Al/La Ca/Al/La/ Ca/Al/La/ Ca/Al/La/ Ca/Al/La/Ca/Al/La/ Ca/Al/La/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Zn/LaSr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Cs/Zn Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Sm/Cs Sm/Cs/ Sm/Cs/ Sm/Cs/ Sm/Cs/ Sm/Cs/ Sm/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ In/K In/K/ In/K/ In/K/ In/K/ In/K/ In/K/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Ho/Cs/Li/La Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Cs/La/Na Cs/La/Na/ Cs/La/Na/ Cs/La/Na/ Cs/La/Na/ Cs/La/Na/Cs/La/Na/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ La/S/Sr La/S/Sr/La/S/Sr/ La/S/Sr/ La/S/Sr/ La/S/Sr/ La/S/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ K/La/Zr/Ag K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/K/La/Zr/Ag/ K/La/Zr/Ag/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Lu/TlLu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Pr/Zn Pr/Zn/ Pr/Zn/ Pr/Zn/ Pr/Zn/ Pr/Zn/ Pr/Zn/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Rb/Sr/La Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Na/Sr/Eu/Ca Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/BSr/B/ Sr/B/ Sr/B/ Sr/B/ Sr/B/ Sr/B/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ Rb/Sr/K/Cs/Sr/La K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/K/Cs/Sr/La/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/Sr/Lu Na/Sr/Lu/Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Eu/Dy Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/Sr/Eu/Dy/ Sr/Eu/Dy/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Lu/Nb Lu/Nb/Lu/Nb/ Lu/Nb/ Lu/Nb/ Lu/Nb/ Lu/Nb/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆La/Dy/Gd La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/Mg/Tl/P Na/Mg/Tl/P/ Na/Mg/Tl/P/Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Na/Pt Na/Pt/ Na/Pt/ Na/Pt/ Na/Pt/ Na/Pt/ Na/Pt/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Gd/Li/K Gd/Li/K/ Gd/Li/K/ Gd/Li/K/Gd/Li/K/ Gd/Li/K/ Gd/Li/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Rb/K/LuRb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/La/Dy/S Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Na/Ce/Co Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/Na/Ce/Co/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/Ce Na/Ce/ Na/Ce/Na/Ce/ Na/Ce/ Na/Ce/ Na/Ce/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Na/Ga/Gd/Al Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Na/Ga/Gd/Al/Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ba/Rh/TaBa/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ba/Ta Ba/Ta/ Ba/Ta/ Ba/Ta/ Ba/Ta/ Ba/Ta/Ba/Ta/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/Al/Bi Na/Al/Bi/Na/Al/Bi/ Na/Al/Bi/ Na/Al/Bi/ Na/Al/Bi/ Na/Al/Bi/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Cs/Eu/S Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/Cs/Eu/S/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sm/Tm/Yb/Fe Sm/Tm/Yb/Fe/Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sm/Tm/Yb Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Hf/Zr/Ta Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Rb/Gd/Li/K Rb/Gd/Li/K/ Rb/Gd/Li/K/Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Gd/Ho/Al/P Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/Gd/Ho/Al/P/ Gd/Ho/Al/P/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/Ca/LuNa/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Cu/Sn Cu/Sn/ Cu/Sn/ Cu/Sn/ Cu/Sn/ Cu/Sn/Cu/Sn/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ag/Au Ag/Au/ Ag/Au/ Ag/Au/Ag/Au/ Ag/Au/ Ag/Au/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Al/Bi Al/Bi/Al/Bi/ Al/Bi/ Al/Bi/ Al/Bi/ Al/Bi/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Al/Mo Al/Mo/ Al/Mo/ Al/Mo/ Al/Mo/ Al/Mo/ Al/Mo/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Al/Nb Al/Nb/ Al/Nb/ Al/Nb/ Al/Nb/ Al/Nb/ Al/Nb/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Au/Pt Au/Pt/ Au/Pt/ Au/Pt/ Au/Pt/ Au/Pt/Au/Pt/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ga/Bi Ga/Bi/ Ga/Bi/ Ga/Bi/Ga/Bi/ Ga/Bi/ Ga/Bi/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Mg/W Mg/W/Mg/W/ Mg/W/ Mg/W/ Mg/W/ Mg/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Pb/Au Pb/Au/ Pb/Au/ Pb/Au/ Pb/Au/ Pb/Au/ Pb/Au/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Sn/Mg Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Zn/Bi Zn/Bi/ Zn/Bi/ Zn/Bi/ Zn/Bi/ Zn/Bi/Zn/Bi/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Ta Sr/Ta/ Sr/Ta/ Sr/Ta/Sr/Ta/ Sr/Ta/ Sr/Ta/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na Na/ Na/Na/ Na/ Na/ Na/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr Sr/ Sr/ Sr/ Sr/Sr/ Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ca Ca/ Ca/ Ca/ Ca/ Ca/ Ca/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Yb Yb/ Yb/ Yb/ Yb/ Yb/ Yb/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Cs Cs/ Cs/ Cs/ Cs/ Cs/ Cs/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sb Sb/ Sb/ Sb/ Sb/ Sb/ Sb/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Gd/Ho Gd/Ho/ Gd/Ho/ Gd/Ho/ Gd/Ho/ Gd/Ho/ Gd/Ho/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Zr/Bi Zr/Bi/ Zr/Bi/ Zr/Bi/ Zr/Bi/Zr/Bi/ Zr/Bi/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ho/Sr Ho/Sr/ Ho/Sr/Ho/Sr/ Ho/Sr/ Ho/Sr/ Ho/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Gd/Ho/Sr Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ca/Sr Ca/Sr/ Ca/Sr/ Ca/Sr/ Ca/Sr/Ca/Sr/ Ca/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ca/Sr/W Ca/Sr/W/Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Na/Zr/Eu/Tm Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Sr/Ho/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Tm/Na La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Sr/Pb Sr/Pb/ Sr/Pb/ Sr/Pb/ Sr/Pb/ Sr/Pb/ Sr/Pb/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Sr/W/Li Sr/W/Li/ Sr/W/Li/ Sr/W/Li/ Sr/W/Li/ Sr/W/Li/Sr/W/Li/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ca/Sr/W Ca/Sr/W/ Ca/Sr/W/Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Sr/Hf Sr/Hf/ Sr/Hf/ Sr/Hf/ Sr/Hf/ Sr/Hf/ Sr/Hf/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Au/Re Au/Re/ Au/Re/ Au/Re/ Au/Re/ Au/Re/Au/Re/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/W Sr/W/ Sr/W/ Sr/W/Sr/W/ Sr/W/ Sr/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ La/Nd La/Nd/La/Nd/ La/Nd/ La/Nd/ La/Nd/ La/Nd/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆La/Sm La/Sm/ La/Sm/ La/Sm/ La/Sm/ La/Sm/ La/Sm/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ La/Ce La/Ce/ La/Ce/ La/Ce/ La/Ce/ La/Ce/ La/Ce/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ La/Sr La/Sr/ La/Sr/ La/Sr/ La/Sr/ La/Sr/La/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ La/Nd/Sr La/Nd/Sr/La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ La/Bi/Sr La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/La/Bi/Sr/ La/Bi/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ La/Ce/Nd/SrLa/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/La/Ce/Nd/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ La/Bi/Ce/Nd/SrLa/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Eu/Gd Eu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Ca/Na Ca/Na/ Ca/Na/ Ca/Na/ Ca/Na/ Ca/Na/ Ca/Na/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Eu/Sm Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/Eu/Sm/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Eu/Sr Eu/Sr/ Eu/Sr/ Eu/Sr/Eu/Sr/ Eu/Sr/ Eu/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Mg/Sr Mg/Sr/Mg/Sr/ Mg/Sr/ Mg/Sr/ Mg/Sr/ Mg/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Ce/Mg Ce/Mg/ Ce/Mg/ Ce/Mg/ Ce/Mg/ Ce/Mg/ Ce/Mg/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Gd/Sm Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Au/Pb Au/Pb/ Au/Pb/ Au/Pb/ Au/Pb/ Au/Pb/Au/Pb/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Bi/Hf Bi/Hf/ Bi/Hf/ Bi/Hf/Bi/Hf/ Bi/Hf/ Bi/Hf/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Rb/S Rb/S/Rb/S/ Rb/S/ Rb/S/ Rb/S/ Rb/S/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Sr/Nd Sr/Nd/ Sr/Nd/ Sr/Nd/ Sr/Nd/ Sr/Nd/ Sr/Nd/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Eu/Y Eu/Y/ Eu/Y/ Eu/Y/ Eu/Y/ Eu/Y/ Eu/Y/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Mg/Nd Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ La/Mg La/Mg/ La/Mg/ La/Mg/ La/Mg/La/Mg/ La/Mg/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Mg/Nd/Fe Mg/Nd/Fe/Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Rb/Sr Rb/Sr/ Rb/Sr/ Rb/Sr/ Rb/Sr/ Rb/Sr/ Rb/Sr/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ Rb/Sr/

TABLE 10 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS (DOP) NW DopLa_(4−X)Nd_(X)O₆* LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Eu/Na Eu/Na/ Eu/Na/ Eu/Na/ Eu/Na/Eu/Na/ Eu/Na/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Na Sr/Na/Sr/Na/ Sr/Na/ Sr/Na/ Sr/Na/ Sr/Na/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Na/Zr/Eu/Ca Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Mg/Na Mg/Na/ Mg/Na/ Mg/Na/ Mg/Na/ Mg/Na/ Mg/Na/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Sm/Ho/Tm Sr/Sm/Ho/Tm/Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/W Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/Sr/W/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Mg/La/K Mg/La/K/ Mg/La/K/ Mg/La/K/Mg/La/K/ Mg/La/K/ Mg/La/K/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/K/Mg/TmNa/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/Dy/K Na/Dy/K/ Na/Dy/K/ Na/Dy/K/Na/Dy/K/ Na/Dy/K/ Na/Dy/K/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/B Sr/B/Sr/B/ Sr/B/ Sr/B/ Sr/B/ Sr/B/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Na/La/Dy Na/La/Dy/ Na/La/Dy/ Na/La/Dy/ Na/La/Dy/Na/La/Dy/ Na/La/Dy/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/La/EuNa/La/Eu/ Na/La/Eu/ Na/La/Eu/ Na/La/Eu/ Na/La/Eu/ Na/La/Eu/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/La/Eu/In Na/La/Eu/In/Na/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/La/K Na/La/K/ Na/La/K/ Na/La/K/Na/La/K/ Na/La/K/ Na/La/K/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/La/Li/CsNa/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/Na/La/Li/Cs/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ K/La K/La/K/La/ K/La/ K/La/ K/La/ K/La/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ K/La/S K/La/S/ K/La/S/ K/La/S/ K/La/S/ K/La/S/K/La/S/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ K/Na K/Na/ K/Na/ K/Na/ K/Na/ K/Na/K/Na/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/Cs Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/Li/Cs/ Li/Cs/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/Cs/LaLi/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/Cs/La/Tm Li/Cs/La/Tm/Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/Cs/Sr/Tm Li/Cs/Sr/Tm/Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/Sr/Cs Li/Sr/Cs/ Li/Sr/Cs/Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Li/Sr/Zn/K Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/Pr Sr/Pr/ Sr/Pr/ Sr/Pr/ Sr/Pr/ Sr/Pr/ Sr/Pr/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/Ga/Cs Li/Ga/Cs/ Li/Ga/Cs/Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Li/K/Sr/La Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Li/Na Li/Na/ Li/Na/ Li/Na/ Li/Na/ Li/Na/ Li/Na/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/Na/Rb/Ga Li/Na/Rb/Ga/Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/Na/Sr Li/Na/Sr/ Li/Na/Sr/Li/Na/Sr/ Li/Na/Sr/ Li/Na/Sr/ Li/Na/Sr/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Li/Na/Sr/La Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Li/Sm/Cs Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/Li/Sm/Cs/ Li/Sm/Cs/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ba/Sm/Yb/SBa/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ba/Tm/K/La Ba/Tm/K/La/ Ba/Tm/K/La/Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Ba/Tm/Zn/K Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Cs/K/La Cs/K/La/ Cs/K/La/ Cs/K/La/ Cs/K/La/ Cs/K/La/Cs/K/La/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Pr/K Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Cs/La/Tm/NaCs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/Cs/La/Tm/Na/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Cs/Li/K/LaCs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sm/Li/Sr/Cs Sm/Li/Sr/Cs/Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Cs/La Sr/Cs/La/ Sr/Cs/La/Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/Tm/Li/Cs Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Zn/K Zn/K/ Zn/K/ Zn/K/ Zn/K/ Zn/K/ Zn/K/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Zr/Cs/K/La Zr/Cs/K/La/ Zr/Cs/K/La/Zr/Cs/K/La/ Zr/Cs/K/La/ Zr/Cs/K/La/ Zr/Cs/K/La/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Rb/Ca/In/Ni Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ Rb/Ca/In/Ni/Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/Ho/Tm Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/Sr/Ho/Tm/ Sr/Ho/Tm/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/Nd/SLa/Nd/S/ La/Nd/S/ La/Nd/S/ La/Nd/S/ La/Nd/S/ La/Nd/S/ La_(4−X)Nd_(X)O₆LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/Hf/Rb Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/Sr/Hf/Rb/ Sr/Hf/Rb/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/Rb/CaLi/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/K Li/K/ Li/K/ Li/K/ Li/K/ Li/K/Li/K/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Tm/Lu/Ta/P Tm/Lu/Ta/P/ Tm/Lu/Ta/P/Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Rb/Ca/Dy/P Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ Rb/Ca/Dy/P/Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Mg/La/Yb/Zn Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Mg/La/Yb/Zn/Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Rb/Sr/Lu Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/Rb/Sr/Lu/ Rb/Sr/Lu/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/Sr/Lu/NbNa/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/Na/Sr/Lu/Nb/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/Eu/HfNa/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Dy/Rb/Gd Dy/Rb/Gd/ Dy/Rb/Gd/Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Na/Pt/Bi Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/Na/Pt/Bi/ Na/Pt/Bi/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Rb/Hf Rb/Hf/Rb/Hf/ Rb/Hf/ Rb/Hf/ Rb/Hf/ Rb/Hf/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Ca/Cs Ca/Cs/ Ca/Cs/ Ca/Cs/ Ca/Cs/ Ca/Cs/ Ca/Cs/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ca/Mg/Na Ca/Mg/Na/ Ca/Mg/Na/Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Hf/Bi Hf/Bi/ Hf/Bi/ Hf/Bi/ Hf/Bi/ Hf/Bi/ Hf/Bi/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Sn Sr/Sn/ Sr/Sn/ Sr/Sn/ Sr/Sn/Sr/Sn/ Sr/Sn/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/W Sr/W/Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/Nb Sr/Nb/ Sr/Nb/ Sr/Nb/ Sr/Nb/ Sr/Nb/ Sr/Nb/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Zr/W Zr/W/ Zr/W/ Zr/W/ Zr/W/ Zr/W/Zr/W/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Hf/K Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Y/W Y/W/ Y/W/Y/W/ Y/W/ Y/W/ Y/W/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/W Na/W/Na/W/ Na/W/ Na/W/ Na/W/ Na/W/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Bi/W Bi/W/ Bi/W/ Bi/W/ Bi/W/ Bi/W/ Bi/W/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Bi/Cs Bi/Cs/ Bi/Cs/ Bi/Cs/ Bi/Cs/Bi/Cs/ Bi/Cs/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Bi/Ca Bi/Ca/Bi/Ca/ Bi/Ca/ Bi/Ca/ Bi/Ca/ Bi/Ca/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Bi/Sn Bi/Sn/ Bi/Sn/ Bi/Sn/ Bi/Sn/ Bi/Sn/ Bi/Sn/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Bi/Sb Bi/Sb/ Bi/Sb/ Bi/Sb/ Bi/Sb/Bi/Sb/ Bi/Sb/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ge/Hf Ge/Hf/Ge/Hf/ Ge/Hf/ Ge/Hf/ Ge/Hf/ Ge/Hf/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Hf/Sm Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sb/Ag Sb/Ag/ Sb/Ag/ Sb/Ag/ Sb/Ag/Sb/Ag/ Sb/Ag/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sb/Bi Sb/Bi/Sb/Bi/ Sb/Bi/ Sb/Bi/ Sb/Bi/ Sb/Bi/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sb/Au Sb/Au/ Sb/Au/ Sb/Au/ Sb/Au/ Sb/Au/ Sb/Au/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Zr Sr/Zr/ Sr/Zr/ Sr/Zr/ Sr/Zr/Sr/Zr/ Sr/Zr/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sb/Sm Sb/Sm/Sb/Sm/ Sb/Sm/ Sb/Sm/ Sb/Sm/ Sb/Sm/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sb/Sr Sb/Sr/ Sb/Sr/ Sb/Sr/ Sb/Sr/ Sb/Sr/ Sb/Sr/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sb/W Sb/W/ Sb/W/ Sb/W/ Sb/W/ Sb/W/Sb/W/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sb/Hf Sb/Hf/ Sb/Hf/ Sb/Hf/ Sb/Hf/Sb/Hf/ Sb/Hf/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sb/Yb Sb/Yb/Sb/Yb/ Sb/Yb/ Sb/Yb/ Sb/Yb/ Sb/Yb/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sb/Sn Sb/Sn/ Sb/Sn/ Sb/Sn/ Sb/Sn/ Sb/Sn/ Sb/Sn/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Yb/Au Yb/Au/ Yb/Au/ Yb/Au/ Yb/Au/Yb/Au/ Yb/Au/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Yb/Ta Yb/Ta/Yb/Ta/ Yb/Ta/ Yb/Ta/ Yb/Ta/ Yb/Ta/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Yb/W Yb/W/ Yb/W/ Yb/W/ Yb/W/ Yb/W/ Yb/W/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Yb/Sr Yb/Sr/ Yb/Sr/ Yb/Sr/ Yb/Sr/Yb/Sr/ Yb/Sr/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Yb/Pb Yb/Pb/Yb/Pb/ Yb/Pb/ Yb/Pb/ Yb/Pb/ Yb/Pb/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Yb/W Yb/W/ Yb/W/ Yb/W/ Yb/W/ Yb/W/ Yb/W/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Yb/Ag Yb/Ag/ Yb/Ag/ Yb/Ag/ Yb/Ag/Yb/Ag/ Yb/Ag/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Au/Sr Au/Sr/Au/Sr/ Au/Sr/ Au/Sr/ Au/Sr/ Au/Sr/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ W/Ge W/Ge/ W/Ge/ W/Ge/ W/Ge/ W/Ge/ W/Ge/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ta/Sr Ta/Sr/ Ta/Sr/ Ta/Sr/ Ta/Sr/Ta/Sr/ Ta/Sr/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ta/Hf Ta/Hf/Ta/Hf/ Ta/Hf/ Ta/Hf/ Ta/Hf/ Ta/Hf/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ W/Au W/Au/ W/Au/ W/Au/ W/Au/ W/Au/ W/Au/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Tb Sr/Tb/ Sr/Tb/ Sr/Tb/ Sr/Tb/Sr/Tb/ Sr/Tb/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ca/W Ca/W/Ca/W/ Ca/W/ Ca/W/ Ca/W/ Ca/W/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Au/Re Au/Re/ Au/Re/ Au/Re/ Au/Re/ Au/Re/ Au/Re/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sm/Li Sm/Li/ Sm/Li/ Sm/Li/ Sm/Li/Sm/Li/ Sm/Li/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/K La/K/La/K/ La/K/ La/K/ La/K/ La/K/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Zn/Cs Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/K/Mg Na/K/Mg/ Na/K/Mg/ Na/K/Mg/Na/K/Mg/ Na/K/Mg/ Na/K/Mg/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Zr/Cs Zr/Cs/Zr/Cs/ Zr/Cs/ Zr/Cs/ Zr/Cs/ Zr/Cs/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Ca/Ce Ca/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/Li/Cs Na/Li/Cs/ Na/Li/Cs/Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Li/Sr Li/Sr/ Li/Sr/ Li/Sr/ Li/Sr/ Li/Sr/ Li/Sr/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/Dy/K La/Dy/K/ La/Dy/K/ La/Dy/K/La/Dy/K/ La/Dy/K/ La/Dy/K/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Dy/K Dy/K/Dy/K/ Dy/K/ Dy/K/ Dy/K/ Dy/K/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ La/Mg La/Mg/ La/Mg/ La/Mg/ La/Mg/ La/Mg/ La/Mg/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/Nd/In/K Na/Nd/In/K/ Na/Nd/In/K/Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ In/Sr In/Sr/ In/Sr/ In/Sr/ In/Sr/ In/Sr/ In/Sr/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Cs Sr/Cs/ Sr/Cs/ Sr/Cs/ Sr/Cs/Sr/Cs/ Sr/Cs/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Ce Sr/Ce/Sr/Ce/ Sr/Ce/ Sr/Ce/ Sr/Ce/ Sr/Ce/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Rb/Ga/Tm/Cs Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Ga/Cs Ga/Cs/ Ga/Cs/ Ga/Cs/ Ga/Cs/ Ga/Cs/ Ga/Cs/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ K/La/Zr/Ag K/La/Zr/Ag/ K/La/Zr/Ag/K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Lu/Fe Lu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Tm Sr/Tm/ Sr/Tm/ Sr/Tm/ Sr/Tm/Sr/Tm/ Sr/Tm/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/Dy La/Dy/La/Dy/ La/Dy/ La/Dy/ La/Dy/ La/Dy/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sm/Li/Sr Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/Sm/Li/Sr/ Sm/Li/Sr/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Zr/KSr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ La_(4−X)Nd_(X)O₆LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Mg/K Mg/K/ Mg/K/ Mg/K/ Mg/K/ Mg/K/ Mg/K/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/Rb/Ga Li/Rb/Ga/ Li/Rb/Ga/Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Li/Cs/Tm Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/Li/Cs/Tm/ Li/Cs/Tm/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Zr/K Zr/K/Zr/K/ Zr/K/ Zr/K/ Zr/K/ Zr/K/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Li/Cs Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/K/La Li/K/La/ Li/K/La/ Li/K/La/Li/K/La/ Li/K/La/ Li/K/La/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ce/Zr/LaCe/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ca/Al/La Ca/Al/La/ Ca/Al/La/Ca/Al/La/ Ca/Al/La/ Ca/Al/La/ Ca/Al/La/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/Zn/La Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/Sr/Zn/La/ Sr/Zn/La/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Cs/ZnSr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sm/Cs Sm/Cs/ Sm/Cs/ Sm/Cs/ Sm/Cs/Sm/Cs/ Sm/Cs/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ In/K In/K/In/K/ In/K/ In/K/ In/K/ In/K/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Ho/Cs/Li/La Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Cs/La/Na Cs/La/Na/ Cs/La/Na/ Cs/La/Na/ Cs/La/Na/Cs/La/Na/ Cs/La/Na/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/S/SrLa/S/Sr/ La/S/Sr/ La/S/Sr/ La/S/Sr/ La/S/Sr/ La/S/Sr/ La_(4−X)Nd_(X)O₆LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ K/La/Zr/Ag K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Lu/Tl Lu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Pr/Zn Pr/Zn/ Pr/Zn/ Pr/Zn/ Pr/Zn/Pr/Zn/ Pr/Zn/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Rb/Sr/LaRb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Ce/K Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/Sr/Eu/CaNa/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/Na/Sr/Eu/Ca/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ K/Cs/Sr/LaK/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/Sr/Lu Na/Sr/Lu/ Na/Sr/Lu/Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/Eu/Dy Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/Sr/Eu/Dy/ Sr/Eu/Dy/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Lu/Nb Lu/Nb/Lu/Nb/ Lu/Nb/ Lu/Nb/ Lu/Nb/ Lu/Nb/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ La/Dy/Gd La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/La/Dy/Gd/ La/Dy/Gd/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/Mg/Tl/PNa/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/Pt Na/Pt/ Na/Pt/ Na/Pt/ Na/Pt/Na/Pt/ Na/Pt/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Gd/Li/KGd/Li/K/ Gd/Li/K/ Gd/Li/K/ Gd/Li/K/ Gd/Li/K/ Gd/Li/K/ La_(4−X)Nd_(X)O₆LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Rb/K/Lu Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/Rb/K/Lu/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/La/Dy/S Sr/La/Dy/S/ Sr/La/Dy/S/Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Na/Ce/Co Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/Na/Ce/Co/ Na/Ce/Co/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/Ce Na/Ce/Na/Ce/ Na/Ce/ Na/Ce/ Na/Ce/ Na/Ce/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Na/Ga/Gd/Al Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Na/Ga/Gd/Al/Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Ba/Rh/Ta Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/Ba/Rh/Ta/ Ba/Rh/Ta/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ba/Ta Ba/Ta/Ba/Ta/ Ba/Ta/ Ba/Ta/ Ba/Ta/ Ba/Ta/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Na/Al/Bi Na/Al/Bi/ Na/Al/Bi/ Na/Al/Bi/ Na/Al/Bi/Na/Al/Bi/ Na/Al/Bi/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Cs/Eu/SCs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ La_(4−X)Nd_(X)O₆LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sm/Tm/Yb/Fe Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sm/Tm/Yb Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/Sm/Tm/Yb/ Sm/Tm/Yb/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Hf/Zr/TaHf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Tb/K Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Rb/Gd/Li/KRb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Gd/Ho/Al/P Gd/Ho/Al/P/ Gd/Ho/Al/P/Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Na/Ca/Lu Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/Na/Ca/Lu/ Na/Ca/Lu/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Cu/Sn Cu/Sn/Cu/Sn/ Cu/Sn/ Cu/Sn/ Cu/Sn/ Cu/Sn/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Ag/Au Ag/Au/ Ag/Au/ Ag/Au/ Ag/Au/ Ag/Au/ Ag/Au/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Al/Bi Al/Bi/ Al/Bi/ Al/Bi/ Al/Bi/Al/Bi/ Al/Bi/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Al/Mo Al/Mo/Al/Mo/ Al/Mo/ Al/Mo/ Al/Mo/ Al/Mo/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Al/Nb Al/Nb/ Al/Nb/ Al/Nb/ Al/Nb/ Al/Nb/ Al/Nb/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Au/Pt Au/Pt/ Au/Pt/ Au/Pt/ Au/Pt/Au/Pt/ Au/Pt/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ga/Bi Ga/Bi/Ga/Bi/ Ga/Bi/ Ga/Bi/ Ga/Bi/ Ga/Bi/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Mg/W Mg/W/ Mg/W/ Mg/W/ Mg/W/ Mg/W/ Mg/W/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Pb/Au Pb/Au/ Pb/Au/ Pb/Au/ Pb/Au/Pb/Au/ Pb/Au/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sn/Mg Sn/Mg/Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Zn/Bi Zn/Bi/ Zn/Bi/ Zn/Bi/ Zn/Bi/ Zn/Bi/ Zn/Bi/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Ta Sr/Ta/ Sr/Ta/ Sr/Ta/ Sr/Ta/Sr/Ta/ Sr/Ta/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na Na/ Na/ Na/Na/ Na/ Na/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr Sr/ Sr/ Sr/Sr/ Sr/ Sr/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ca Ca/ Ca/ Ca/Ca/ Ca/ Ca/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Yb Yb/ Yb/ Yb/Yb/ Yb/ Yb/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Cs Cs/ Cs/ Cs/Cs/ Cs/ Cs/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sb Sb/ Sb/ Sb/Sb/ Sb/ Sb/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Gd/Ho Gd/Ho/Gd/Ho/ Gd/Ho/ Gd/Ho/ Gd/Ho/ Gd/Ho/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Zr/Bi Zr/Bi/ Zr/Bi/ Zr/Bi/ Zr/Bi/ Zr/Bi/ Zr/Bi/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ho/Sr Ho/Sr/ Ho/Sr/ Ho/Sr/ Ho/Sr/Ho/Sr/ Ho/Sr/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Gd/Ho/SrGd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ca/Sr Ca/Sr/ Ca/Sr/ Ca/Sr/ Ca/Sr/Ca/Sr/ Ca/Sr/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ca/Sr/WCa/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ La_(4−X)Nd_(X)O₆LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Na/Zr/Eu/Tm Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/Ho/Tm/Na Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/Pb Sr/Pb/ Sr/Pb/ Sr/Pb/ Sr/Pb/ Sr/Pb/ Sr/Pb/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/W/Li Sr/W/Li/ Sr/W/Li/ Sr/W/Li/Sr/W/Li/ Sr/W/Li/ Sr/W/Li/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ca/Sr/WCa/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ La_(4−X)Nd_(X)O₆LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/Hf Sr/Hf/ Sr/Hf/ Sr/Hf/ Sr/Hf/ Sr/Hf/ Sr/Hf/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Au/Re Au/Re/ Au/Re/ Au/Re/ Au/Re/Au/Re/ Au/Re/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/W Sr/W/Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ La/Nd La/Nd/ La/Nd/ La/Nd/ La/Nd/ La/Nd/ La/Nd/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/Sm La/Sm/ La/Sm/ La/Sm/ La/Sm/La/Sm/ La/Sm/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/Ce La/Ce/La/Ce/ La/Ce/ La/Ce/ La/Ce/ La/Ce/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ La/Sr La/Sr/ La/Sr/ La/Sr/ La/Sr/ La/Sr/ La/Sr/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/Nd/Sr La/Nd/Sr/ La/Nd/Sr/La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ La/Bi/Sr La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/La/Bi/Sr/ La/Bi/Sr/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/Ce/Nd/SrLa/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/La/Ce/Nd/Sr/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/Bi/Ce/Nd/SrLa/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Eu/Gd Eu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ca/Na Ca/Na/ Ca/Na/ Ca/Na/ Ca/Na/Ca/Na/ Ca/Na/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Eu/Sm Eu/Sm/Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Eu/Sr Eu/Sr/ Eu/Sr/ Eu/Sr/ Eu/Sr/ Eu/Sr/ Eu/Sr/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Mg/Sr Mg/Sr/ Mg/Sr/ Mg/Sr/ Mg/Sr/Mg/Sr/ Mg/Sr/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ce/Mg Ce/Mg/Ce/Mg/ Ce/Mg/ Ce/Mg/ Ce/Mg/ Ce/Mg/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Gd/Sm Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Au/Pb Au/Pb/ Au/Pb/ Au/Pb/ Au/Pb/Au/Pb/ Au/Pb/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Bi/Hf Bi/Hf/Bi/Hf/ Bi/Hf/ Bi/Hf/ Bi/Hf/ Bi/Hf/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Rb/S Rb/S/ Rb/S/ Rb/S/ Rb/S/ Rb/S/ Rb/S/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Nd Sr/Nd/ Sr/Nd/ Sr/Nd/ Sr/Nd/Sr/Nd/ Sr/Nd/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Eu/Y Eu/Y/Eu/Y/ Eu/Y/ Eu/Y/ Eu/Y/ Eu/Y/ La_(4−X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Mg/Nd Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/Mg La/Mg/ La/Mg/ La/Mg/ La/Mg/La/Mg/ La/Mg/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Mg/Nd/FeMg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Rb/Sr Rb/Sr/ Rb/Sr/ Rb/Sr/ Rb/Sr/Rb/Sr/ Rb/Sr/ La_(4−X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ *x is a numberranging from greater than 0 to less than 4

TABLE 11 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS (DOP) NW DopLa_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Eu/Na Eu/Na/ Eu/Na/ Eu/Na/Eu/Na/ Eu/Na/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Na Sr/Na/Sr/Na/ Sr/Na/ Sr/Na/ Sr/Na/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaNa/Zr/Eu/Ca Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/Na/Zr/Eu/Ca/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—Laa Ce—La Mg/Na Mg/Na/Mg/Na/ Mg/Na/ Mg/Na/ Mg/Na/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaSr/Sm/Ho/Tm Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/Sr/Sm/Ho/Tm/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/W Sr/W/ Sr/W/Sr/W/ Sr/W/ Sr/W/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Mg/La/KMg/La/K/ Mg/La/K/ Mg/La/K/ Mg/La/K/ Mg/La/K/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Na/K/Mg/Tm Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/Na/K/Mg/Tm/ Na/K/Mg/Tm/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaNa/Dy/K Na/Dy/K/ Na/Dy/K/ Na/Dy/K/ Na/Dy/K/ Na/Dy/K/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Na/La/Dy Na/La/Dy/ Na/La/Dy/ Na/La/Dy/ Na/La/Dy/Na/La/Dy/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Na/La/Eu Na/La/Eu/Na/La/Eu/ Na/La/Eu/ Na/La/Eu/ Na/La/Eu/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Na/La/Eu/In Na/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/Na/La/Eu/In/ Na/La/Eu/In/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaNa/La/K Na/La/K/ Na/La/K/ Na/La/K/ Na/La/K/ Na/La/K/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Na/La/Li/Cs Na/La/Li/Cs/ Na/La/Li/Cs/Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La K/La K/La/ K/La/ K/La/ K/La/ K/La/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La K/La/S K/La/S/ K/La/S/ K/La/S/ K/La/S/ K/La/S/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La K/Na K/Na/ K/Na/ K/Na/ K/Na/K/Na/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Cs Li/Cs/ Li/Cs/Li/Cs/ Li/Cs/ Li/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Cs/LaLi/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Sr/Pr/K Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/Sr/Pr/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Cs/La/TmLi/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Cs/Sr/Tm Li/Cs/Sr/Tm/Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Li/Sr/Cs Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/Li/Sr/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Sr/Zn/KLi/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Ga/Cs Li/Ga/Cs/ Li/Ga/Cs/Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaLi/K/Sr/La Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Na Li/Na/ Li/Na/ Li/Na/Li/Na/ Li/Na/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Na/Rb/GaLi/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Na/Sr Li/Na/Sr/ Li/Na/Sr/Li/Na/Sr/ Li/Na/Sr/ Li/Na/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaLi/Na/Sr/La Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/Li/Na/Sr/La/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Sm/CsLi/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Ba/Sm/Yb/S Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaBa/Tm/K/La Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ba/Tm/Zn/K Ba/Tm/Zn/K/Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Sr/Tb/K Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La C + s/K/La Cs/K/La/ Cs/K/La/Cs/K/La/ Cs/K/La/ Cs/K/La/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaCs/La/Tm/Na Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/Cs/La/Tm/Na/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Cs/Li/K/LaCs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sm/Li/Sr/Cs Sm/Li/Sr/Cs/Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Sr/Cs/La Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/Sr/Cs/La/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Tm/Li/CsSr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Zn/K Zn/K/ Zn/K/ Zn/K/ Zn/K/Zn/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Zr/Cs/K/La Zr/Cs/K/La/Zr/Cs/K/La/ Zr/Cs/K/La/ Zr/Cs/K/La/ Zr/Cs/K/La/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Rb/Ca/In/Ni Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ Rb/Ca/In/Ni/Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaSr/Ho/Tm Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La La/Nd/S La/Nd/S/ La/Nd/S/La/Nd/S/ La/Nd/S/ La/Nd/S/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaLi/Rb/Ca Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/K Li/K/ Li/K/ Li/K/ Li/K/Li/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Tm/Lu/Ta/P Tm/Lu/Ta/P/Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Rb/Ca/Dy/P Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ Rb/Ca/Dy/P/Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaMg/La/Yb/Zn Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Mg/La/Yb/Zn/Mg/La/Yb/Zn/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Rb/Sr/LuRb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Sr/B Sr/B/ Sr/B/ Sr/B/ Sr/B/ Sr/B/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Na/Sr/Lu/Nb Na/Sr/Lu/Nb/Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Na/Eu/Hf Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/Na/Eu/Hf/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Dy/Rb/Gd Dy/Rb/Gd/Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Na/Pt/Bi Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Rb/Hf Rb/Hf/ Rb/Hf/ Rb/Hf/Rb/Hf/ Rb/Hf/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ca/Cs Ca/Cs/Ca/Cs/ Ca/Cs/ Ca/Cs/ Ca/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaCa/Mg/Na Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Hf/Bi Hf/Bi/ Hf/Bi/ Hf/Bi/Hf/Bi/ Hf/Bi/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Sn Sr/Sn/Sr/Sn/ Sr/Sn/ Sr/Sn/ Sr/Sn/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaSr/W Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La Sr/Nb Sr/Nb/ Sr/Nb/ Sr/Nb/ Sr/Nb/ Sr/Nb/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Zr/W Zr/W/ Zr/W/ Zr/W/ Zr/W/ Zr/W/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Y/W Y/W/ Y/W/ Y/W/ Y/W/ Y/W/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Na/W Na/W/ Na/W/ Na/W/ Na/W/ Na/W/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Bi/W Bi/W/ Bi/W/ Bi/W/ Bi/W/Bi/W/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Bi/Cs Bi/Cs/ Bi/Cs/Bi/Cs/ Bi/Cs/ Bi/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Bi/CaBi/Ca/ Bi/Ca/ Bi/Ca/ Bi/Ca/ Bi/Ca/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La Sr/Pr Sr/Pr/ Sr/Pr/ Sr/Pr/ Sr/Pr/ Sr/Pr/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Bi/Sn Bi/Sn/ Bi/Sn/ Bi/Sn/ Bi/Sn/ Bi/Sn/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Bi/Sb Bi/Sb/ Bi/Sb/ Bi/Sb/Bi/Sb/ Bi/Sb/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ge/Hf Ge/Hf/Ge/Hf/ Ge/Hf/ Ge/Hf/ Ge/Hf/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaHf/Sm Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Sb/Ag Sb/Ag/ Sb/Ag/ Sb/Ag/ Sb/Ag/ Sb/Ag/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Sb/Bi Sb/Bi/ Sb/Bi/ Sb/Bi/ Sb/Bi/ Sb/Bi/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sb/Au Sb/Au/ Sb/Au/ Sb/Au/Sb/Au/ Sb/Au/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sb/Sm Sb/Sm/Sb/Sm/ Sb/Sm/ Sb/Sm/ Sb/Sm/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaSb/Sr Sb/Sr/ Sb/Sr/ Sb/Sr/ Sb/Sr/ Sb/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Sb/W Sb/W/ Sb/W/ Sb/W/ Sb/W/ Sb/W/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Sb/Hf Sb/Hf/ Sb/Hf/ Sb/Hf/ Sb/Hf/ Sb/Hf/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sb/Yb Sb/Yb/ Sb/Yb/ Sb/Yb/Sb/Yb/ Sb/Yb/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Hf/K Sr/Hf/K/Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La Sb/Sn Sb/Sn/ Sb/Sn/ Sb/Sn/ Sb/Sn/ Sb/Sn/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Yb/Au Yb/Au/ Yb/Au/ Yb/Au/ Yb/Au/ Yb/Au/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Yb/Ta Yb/Ta/ Yb/Ta/ Yb/Ta/Yb/Ta/ Yb/Ta/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Yb/W Yb/W/ Yb/W/Yb/W/ Yb/W/ Yb/W/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Yb/Sr Yb/Sr/Yb/Sr/ Yb/Sr/ Yb/Sr/ Yb/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaYb/Pb Yb/Pb/ Yb/Pb/ Yb/Pb/ Yb/Pb/ Yb/Pb/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Yb/W Yb/W/ Yb/W/ Yb/W/ Yb/W/ Yb/W/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Yb/Ag Yb/Ag/ Yb/Ag/ Yb/Ag/ Yb/Ag/ Yb/Ag/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Au/Sr Au/Sr/ Au/Sr/ Au/Sr/Au/Sr/ Au/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La W/Ge W/Ge/ W/Ge/W/Ge/ W/Ge/ W/Ge/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Hf/RbSr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Ta/Sr Ta/Sr/ Ta/Sr/ Ta/Sr/ Ta/Sr/ Ta/Sr/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ta/Hf Ta/Hf/ Ta/Hf/ Ta/Hf/Ta/Hf/ Ta/Hf/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La W/Au W/Au/ W/Au/W/Au/ W/Au/ W/Au/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ca/W Ca/W/Ca/W/ Ca/W/ Ca/W/ Ca/W/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Au/ReAu/Re/ Au/Re/ Au/Re/ Au/Re/ Au/Re/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La Sm/Li Sm/Li/ Sm/Li/ Sm/Li/ Sm/Li/ Sm/Li/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La La/K La/K/ La/K/ La/K/ La/K/ La/K/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Zn/Cs Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Na/K/Mg Na/K/Mg/ Na/K/Mg/Na/K/Mg/ Na/K/Mg/ Na/K/Mg/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaZr/Cs Zr/Cs/ Zr/Cs/ Zr/Cs/ Zr/Cs/ Zr/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Ca/Ce Ca/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Sr/Zr/K Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/Sr/Zr/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Na/Li/Cs Na/Li/Cs/Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Li/Sr Li/Sr/ Li/Sr/ Li/Sr/ Li/Sr/ Li/Sr/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La La/Dy/K La/Dy/K/ La/Dy/K/ La/Dy/K/ La/Dy/K/La/Dy/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Dy/K Dy/K/ Dy/K/Dy/K/ Dy/K/ Dy/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La La/Mg La/Mg/La/Mg/ La/Mg/ La/Mg/ La/Mg/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaNa/Nd/In/K Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La In/Sr In/Sr/ In/Sr/ In/Sr/In/Sr/ In/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Cs Sr/Cs/Sr/Cs/ Sr/Cs/ Sr/Cs/ Sr/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaRb/Ga/Tm/Cs Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/Rb/Ga/Tm/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ga/Cs Ga/Cs/Ga/Cs/ Ga/Cs/ Ga/Cs/ Ga/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaK/La/Zr/Ag K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Zr Sr/Zr/ Sr/Zr/ Sr/Zr/Sr/Zr/ Sr/Zr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Lu/Fe Lu/Fe/Lu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaSr/Tm Sr/Tm/ Sr/Tm/ Sr/Tm/ Sr/Tm/ Sr/Tm/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La La/Dy La/Dy/ La/Dy/ La/Dy/ La/Dy/ La/Dy/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Sm/Li/Sr Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/Sm/Li/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Mg/K Mg/K/ Mg/K/Mg/K/ Mg/K/ Mg/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Rb/GaLi/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Li/Cs/Tm Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/Li/Cs/Tm/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Zr/K Zr/K/ Zr/K/Zr/K/ Zr/K/ Zr/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Cs Li/Cs/Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaSr/Ce Sr/Ce/ Sr/Ce/ Sr/Ce/ Sr/Ce/ Sr/Ce/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Li/K/La Li/K/La/ Li/K/La/ Li/K/La/ Li/K/La/ Li/K/La/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ce/Zr/La Ce/Zr/La/ Ce/Zr/La/Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaCa/Al/La Ca/Al/La/ Ca/Al/La/ Ca/Al/La/ Ca/Al/La/ Ca/Al/La/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Zn/La Sr/Zn/La/ Sr/Zn/La/Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaSr/Cs/Zn Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sm/Cs Sm/Cs/ Sm/Cs/ Sm/Cs/Sm/Cs/ Sm/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La In/K In/K/ In/K/In/K/ In/K/ In/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ho/Cs/Li/LaHo/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Cs/La/Na Cs/La/Na/ Cs/La/Na/Cs/La/Na/ Cs/La/Na/ Cs/La/Na/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaLa/S/Sr La/S/Sr/ La/S/Sr/ La/S/Sr/ La/S/Sr/ La/S/Sr/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La K/La/Zr/Ag K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/K/La/Zr/Ag/ K/La/Zr/Ag/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Lu/TlLu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La Pr/Zn Pr/Zn/ Pr/Zn/ Pr/Zn/ Pr/Zn/ Pr/Zn/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Rb/Sr/La Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/Rb/Sr/La/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Na/Sr/Eu/CaNa/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La K/Cs/Sr/La K/Cs/Sr/La/K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Na/Sr/Lu Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/Na/Sr/Lu/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Eu/Dy Sr/Eu/Dy/Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Lu/Nb Lu/Nb/ Lu/Nb/ Lu/Nb/ Lu/Nb/ Lu/Nb/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Sr/Tb Sr/Tb/ Sr/Tb/ Sr/Tb/ Sr/Tb/ Sr/Tb/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La La/Dy/Gd La/Dy/Gd/ La/Dy/Gd/La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaNa/Mg/Tl/P Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Na/Pt Na/Pt/ Na/Pt/ Na/Pt/Na/Pt/ Na/Pt/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Gd/Li/K Gd/Li/K/Gd/Li/K/ Gd/Li/K/ Gd/Li/K/ Gd/Li/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La Rb/K/Lu Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/La/Dy/S Sr/La/Dy/S/Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Na/Ce/Co Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/Na/Ce/Co/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Na/Ce Na/Ce/ Na/Ce/Na/Ce/ Na/Ce/ Na/Ce/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaNa/Ga/Gd/Al Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Na/Ga/Gd/Al/Na/Ga/Gd/Al/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ba/Rh/TaBa/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Ba/Ta Ba/Ta/ Ba/Ta/ Ba/Ta/ Ba/Ta/ Ba/Ta/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Na/Al/Bi Na/Al/Bi/ Na/Al/Bi/Na/Al/Bi/ Na/Al/Bi/ Na/Al/Bi/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaCs/Eu/S Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Sm/Tm/Yb/Fe Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Sm/Tm/Yb Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Hf/Zr/Ta Hf/Zr/Ta/ Hf/Zr/Ta/Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaRb/Gd/Li/K Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—Lai/K Ce—La Gd/Ho/Al/P Gd/Ho/Al/P/Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Na/Ca/Lu Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/Na/Ca/Lu/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Cu/Sn Cu/Sn/ Cu/Sn/Cu/Sn/ Cu/Sn/ Cu/Sn/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ag/AuAg/Au/ Ag/Au/ Ag/Au/ Ag/Au/ Ag/Au/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La Al/Bi Al/Bi/ Al/Bi/ Al/Bi/ Al/Bi/ Al/Bi/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Al/Mo Al/Mo/ Al/Mo/ Al/Mo/ Al/Mo/ Al/Mo/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Al/Nb Al/Nb/ Al/Nb/ Al/Nb/Al/Nb/ Al/Nb/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Ce/K Sr/Ce/K/Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La Au/Pt Au/Pt/ Au/Pt/ Au/Pt/ Au/Pt/ Au/Pt/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Ga/Bi Ga/Bi/ Ga/Bi/ Ga/Bi/ Ga/Bi/ Ga/Bi/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Mg/W Mg/W/ Mg/W/ Mg/W/ Mg/W/Mg/W/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Pb/Au Pb/Au/ Pb/Au/Pb/Au/ Pb/Au/ Pb/Au/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sn/MgSn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La Zn/Bi Zn/Bi/ Zn/Bi/ Zn/Bi/ Zn/Bi/ Zn/Bi/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Sr/Ta Sr/Ta/ Sr/Ta/ Sr/Ta/ Sr/Ta/ Sr/Ta/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Na Na/ Na/ Na/ Na/ Na/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr Sr/ Sr/ Sr/ Sr/ Sr/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ca Ca/ Ca/ Ca/ Ca/ Ca/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Yb Yb/ Yb/ Yb/ Yb/ Yb/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Cs Cs/ Cs/ Cs/ Cs/ Cs/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sb Sb/ Sb/ Sb/ Sb/ Sb/La_(3.8)Nd_(0.2)O₆/ Y—La/ Zr—La/ Pr—La/ Ce—La/ Zn/Bi Zn/Bi Zn/Bi Zn/BiZn/Bi Gd/Ho Gd/Ho/ Gd/Ho/ Gd/Ho/ Gd/Ho/ Gd/Ho/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Zr/Bi Zr/Bi/ Zr/Bi/ Zr/Bi/ Zr/Bi/ Zr/Bi/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ho/Sr Ho/Sr/ Ho/Sr/ Ho/Sr/Ho/Sr/ Ho/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Gd/Ho/SrGd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Ca/Sr Ca/Sr/ Ca/Sr/ Ca/Sr/ Ca/Sr/ Ca/Sr/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ca/Sr/W Ca/Sr/W/ Ca/Sr/W/Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaNa/Zr/Eu/Tm Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/Na/Zr/Eu/Tm/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Ho/Tm/NaSr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Pb Sr/Pb/ Sr/Pb/ Sr/Pb/Sr/Pb/ Sr/Pb/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/W/Li Sr/W/Li/Sr/W/Li/ Sr/W/Li/ Sr/W/Li/ Sr/W/Li/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La Ca/Sr/W Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Hf Sr/Hf/ Sr/Hf/ Sr/Hf/Sr/Hf/ Sr/Hf/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Au/Re Au/Re/Au/Re/ Au/Re/ Au/Re/ Au/Re/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaSr/W Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La La/Nd La/Nd/ La/Nd/ La/Nd/ La/Nd/ La/Nd/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La La/Sm La/Sm/ La/Sm/ La/Sm/ La/Sm/ La/Sm/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La La/Ce La/Ce/ La/Ce/ La/Ce/La/Ce/ La/Ce/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La La/Sr La/Sr/La/Sr/ La/Sr/ La/Sr/ La/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaLa/Nd/Sr La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La La/Bi/Sr La/Bi/Sr/ La/Bi/Sr/La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaLa/Ce/Nd/Sr La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/La/Ce/Nd/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La La/Bi/Ce/Nd/SrLa/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/La/Bi/Ce/Nd/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Eu/Gd Eu/Gd/Eu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaCa/Na Ca/Na/ Ca/Na/ Ca/Na/ Ca/Na/ Ca/Na/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Eu/Sm Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Eu/Sr Eu/Sr/ Eu/Sr/ Eu/Sr/ Eu/Sr/ Eu/Sr/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Mg/Sr Mg/Sr/ Mg/Sr/ Mg/Sr/Mg/Sr/ Mg/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ce/Mg Ce/Mg/Ce/Mg/ Ce/Mg/ Ce/Mg/ Ce/Mg/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaGd/Sm Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Au/Pb Au/Pb/ Au/Pb/ Au/Pb/ Au/Pb/ Au/Pb/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Bi/Hf Bi/Hf/ Bi/Hf/ Bi/Hf/ Bi/Hf/ Bi/Hf/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Rb/S Rb/S/ Rb/S/ Rb/S/ Rb/S/Rb/S/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Nd Sr/Nd/ Sr/Nd/Sr/Nd/ Sr/Nd/ Sr/Nd/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Eu/YEu/Y/ Eu/Y/ Eu/Y/ Eu/Y/ Eu/Y/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaMg/Nd Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La La/Mg La/Mg/ La/Mg/ La/Mg/ La/Mg/ La/Mg/ La_(3.8)Nd_(0.2)O₆N Y—La Zr—La Pr—La Ce—La Mg/Nd/Fe Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/Mg/Nd/Fe/ Mg/Nd/Fe/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Rb/SrRb/Sr/ Rb/Sr/ Rb/Sr/ Rb/Sr/ Rb/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La

TABLE 12 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS (DOP) NW DopLn1_(4−x)Ln2_(x)O₆* La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Eu/Na Eu/Na/ Eu/Na/Eu/Na/ Eu/Na/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Na Sr/Na/Sr/Na/ Sr/Na/ Sr/Na/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgONa/Zr/Eu/Ca Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Mg/Na Mg/Na/ Mg/Na/ Mg/Na/Mg/Na/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Sm/Ho/TmSr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/W Sr/W/ Sr/W/ Sr/W/ Sr/W/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Mg/La/K Mg/La/K/ Mg/La/K/Mg/La/K/ Mg/La/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgONa/K/Mg/Tm Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/Dy/K Na/Dy/K/ Na/Dy/K/Na/Dy/K/ Na/Dy/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/La/DyNa/La/Dy/ Na/La/Dy/ Na/La/Dy/ Na/La/Dy/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/La/Eu Na/La/Eu/ Na/La/Eu/ Na/La/Eu/Na/La/Eu/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/La/Eu/InNa/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/La/K Na/La/K/ Na/La/K/ Na/La/K/ Na/La/K/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/La/Li/Cs Na/La/Li/Cs/Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO K/La K/La/ K/La/ K/La/ K/La/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO K/La/S K/La/S/ K/La/S/K/La/S/ K/La/S/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO K/Na K/Na/K/Na/ K/Na/ K/Na/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/CsLi/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Li/Cs/La Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/Cs/La/Tm Li/Cs/La/Tm/ Li/Cs/La/Tm/Li/Cs/La/Tm/ Li/Cs/La/Tm/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOLi/Cs/Sr/Tm Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/Sr/Cs Li/Sr/Cs/Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Li/Sr/Zn/K Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/Ga/Cs Li/Ga/Cs/Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Li/K/Sr/La Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/Na Li/Na/ Li/Na/ Li/Na/Li/Na/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/Na/Rb/GaLi/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Zr Sr/Zr/ Sr/Zr/ Sr/Zr/ Sr/Zr/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/Na/Sr Li/Na/Sr/Li/Na/Sr/ Li/Na/Sr/ Li/Na/Sr/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Li/Na/Sr/La Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/Sm/Cs Li/Sm/Cs/Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Ba/Sm/Yb/S Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ba/Tm/K/La Ba/Tm/K/La/Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Ba/Tm/Zn/K Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Cs/K/La Cs/K/La/ Cs/K/La/Cs/K/La/ Cs/K/La/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOCs/La/Tm/Na Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Cs/Li/K/La Cs/Li/K/La/Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Sm/Li/Sr/Cs Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Cs/La Sr/Cs/La/Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Sr/Tm/Li/Cs Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Zn/K Zn/K/ Zn/K/ Zn/K/Zn/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Zr/Cs/K/LaZr/Cs/K/La/ Zr/Cs/K/La/ Zr/Cs/K/La/ Zr/Cs/K/La/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Rb/Ca/In/Ni Rb/Ca/In/Ni/ Rb/Ca/In/Ni/Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOSr/Ho/Tm Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/Nd/S La/Nd/S/ La/Nd/S/ La/Nd/S/ La/Nd/S/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Tb Sr/Tb/ Sr/Tb/ Sr/Tb/Sr/Tb/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/Rb/Ca Li/Rb/Ca/Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Li/K Li/K/ Li/K/ Li/K/ Li/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Tm/Lu/Ta/P Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ Tm/Lu/Ta/P/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Rb/Ca/Dy/P Rb/Ca/Dy/P/Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Mg/La/Yb/Zn Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Mg/La/Yb/Zn/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Rb/Sr/Lu Rb/Sr/Lu/Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Na/Sr/Lu/Nb Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/Eu/Hf Na/Eu/Hf/Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Dy/Rb/Gd Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/Pt/Bi Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/Na/Pt/Bi/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Rb/Hf Rb/Hf/Rb/Hf/ Rb/Hf/ Rb/Hf/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ca/CsCa/Cs/ Ca/Cs/ Ca/Cs/ Ca/Cs/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Ca/Mg/Na Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Hf/Bi Hf/Bi/ Hf/Bi/ Hf/Bi/ Hf/Bi/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Sn Sr/Sn/ Sr/Sn/ Sr/Sn/Sr/Sn/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/W Sr/W/ Sr/W/Sr/W/ Sr/W/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Nb Sr/Nb/Sr/Nb/ Sr/Nb/ Sr/Nb/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Zr/WZr/W/ Zr/W/ Zr/W/ Zr/W/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOY/W Y/W/ Y/W/ Y/W/ Y/W/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgONa/W Na/W/ Na/W/ Na/W/ Na/W/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Sr/Ce Sr/Ce/ Sr/Ce/ Sr/Ce/ Sr/Ce/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Bi/W Bi/W/ Bi/W/ Bi/W/ Bi/W/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Bi/Cs Bi/Cs/ Bi/Cs/ Bi/Cs/Bi/Cs/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Bi/Ca Bi/Ca/ Bi/Ca/Bi/Ca/ Bi/Ca/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Bi/Sn Bi/Sn/Bi/Sn/ Bi/Sn/ Bi/Sn/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Bi/SbBi/Sb/ Bi/Sb/ Bi/Sb/ Bi/Sb/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Ge/Hf Ge/Hf/ Ge/Hf/ Ge/Hf/ Ge/Hf/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Hf/Sm Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sb/Ag Sb/Ag/ Sb/Ag/ Sb/Ag/Sb/Ag/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sb/Bi Sb/Bi/ Sb/Bi/Sb/Bi/ Sb/Bi/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sb/Au Sb/Au/Sb/Au/ Sb/Au/ Sb/Au/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sb/SmSb/Sm/ Sb/Sm/ Sb/Sm/ Sb/Sm/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Sb/Sr Sb/Sr/ Sb/Sr/ Sb/Sr/ Sb/Sr/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sb/W Sb/W/ Sb/W/ Sb/W/ Sb/W/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sb/Hf Sb/Hf/ Sb/Hf/ Sb/Hf/Sb/Hf/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sb/Yb Sb/Yb/ Sb/Yb/Sb/Yb/ Sb/Yb/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Pr/KSr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Sb/Sn Sb/Sn/ Sb/Sn/ Sb/Sn/ Sb/Sn/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Yb/Au Yb/Au/ Yb/Au/ Yb/Au/ Yb/Au/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Yb/Ta Yb/Ta/ Yb/Ta/ Yb/Ta/Yb/Ta/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Yb/W Yb/W/ Yb/W/Yb/W/ Yb/W/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Yb/Sr Yb/Sr/Yb/Sr/ Yb/Sr/ Yb/Sr/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Yb/PbYb/Pb/ Yb/Pb/ Yb/Pb/ Yb/Pb/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Yb/W Yb/W/ Yb/W/ Yb/W/ Yb/W/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Yb/Ag Yb/Ag/ Yb/Ag/ Yb/Ag/ Yb/Ag/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Au/Sr Au/Sr/ Au/Sr/ Au/Sr/ Au/Sr/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO W/Ge W/Ge/ W/Ge/ W/Ge/W/Ge/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ta/Sr Ta/Sr/ Ta/Sr/Ta/Sr/ Ta/Sr/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ta/Hf Ta/Hf/Ta/Hf/ Ta/Hf/ Ta/Hf/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO W/AuW/Au/ W/Au/ W/Au/ W/Au/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOCa/W Ca/W/ Ca/W/ Ca/W/ Ca/W/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Au/Re Au/Re/ Au/Re/ Au/Re/ Au/Re/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sm/Li Sm/Li/ Sm/Li/ Sm/Li/ Sm/Li/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/K La/K/ La/K/ La/K/La/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Zn/Cs Zn/Cs/ Zn/Cs/Zn/Cs/ Zn/Cs/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Zr/KSr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Na/K/Mg Na/K/Mg/ Na/K/Mg/ Na/K/Mg/ Na/K/Mg/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Zr/Cs Zr/Cs/ Zr/Cs/ Zr/Cs/ Zr/Cs/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ca/Ce Ca/Ce/ Ca/Ce/ Ca/Ce/Ca/Ce/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/Li/Cs Na/Li/Cs/Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Li/Sr Li/Sr/ Li/Sr/ Li/Sr/ Li/Sr/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/Dy/K La/Dy/K/ La/Dy/K/ La/Dy/K/ La/Dy/K/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Dy/K Dy/K/ Dy/K/ Dy/K/Dy/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/Mg La/Mg/ La/Mg/La/Mg/ La/Mg/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/Nd/In/KNa/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO In/Sr In/Sr/ In/Sr/ In/Sr/ In/Sr/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Cs Sr/Cs/ Sr/Cs/ Sr/Cs/Sr/Cs/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Rb/Ga/Tm/CsRb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ga/Cs Ga/Cs/ Ga/Cs/ Ga/Cs/ Ga/Cs/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO K/La/Zr/Ag K/La/Zr/Ag/K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Lu/Fe Lu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Tm Sr/Tm/ Sr/Tm/ Sr/Tm/ Sr/Tm/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/Dy La/Dy/ La/Dy/ La/Dy/La/Dy/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sm/Li/Sr Sm/Li/Sr/Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Mg/K Mg/K/ Mg/K/ Mg/K/ Mg/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Li/Rb/Ga Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Ce/K Sr/Ce/K/ Sr/Ce/K/Sr/Ce/K/ Sr/Ce/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/Cs/TmLi/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Zr/K Zr/K/ Zr/K/ Zr/K/ Zr/K/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/Cs Li/Cs/ Li/Cs/ Li/Cs/Li/Cs/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/K/La Li/K/La/Li/K/La/ Li/K/La/ Li/K/La/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOCe/Zr/La Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ca/Al/La Ca/Al/La/ Ca/Al/La/ Ca/Al/La/Ca/Al/La/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Zn/LaSr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Cs/Zn Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/Sr/Cs/Zn/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sm/Cs Sm/Cs/Sm/Cs/ Sm/Cs/ Sm/Cs/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO In/KIn/K/ In/K/ In/K/ In/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOSr/Pr Sr/Pr/ Sr/Pr/ Sr/Pr/ Sr/Pr/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Ho/Cs/Li/La Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Cs/La/Na Cs/La/Na/Cs/La/Na/ Cs/La/Na/ Cs/La/Na/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO La/S/Sr La/S/Sr/ La/S/Sr/ La/S/Sr/ La/S/Sr/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO K/La/Zr/Ag K/La/Zr/Ag/ K/La/Zr/Ag/K/La/Zr/Ag/ K/La/Zr/Ag/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOLu/Tl Lu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Pr/Zn Pr/Zn/ Pr/Zn/ Pr/Zn/ Pr/Zn/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Rb/Sr/La Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/Rb/Sr/La/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/Sr/Eu/CaNa/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO K/Cs/Sr/La K/Cs/Sr/La/ K/Cs/Sr/La/K/Cs/Sr/La/ K/Cs/Sr/La/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgONa/Sr/Lu Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Eu/Dy Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/Sr/Eu/Dy/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Lu/Nb Lu/Nb/Lu/Nb/ Lu/Nb/ Lu/Nb/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOLa/Dy/Gd La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/Mg/Tl/P Na/Mg/Tl/P/ Na/Mg/Tl/P/Na/Mg/Tl/P/ Na/Mg/Tl/P/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgONa/Pt Na/Pt/ Na/Pt/ Na/Pt/ Na/Pt/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Gd/Li/K Gd/Li/K/ Gd/Li/K/ Gd/Li/K/ Gd/Li/K/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Rb/K/Lu Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/La/Dy/S Sr/La/Dy/S/Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Na/Ce/Co Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/Ce Na/Ce/ Na/Ce/ Na/Ce/Na/Ce/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Tb/K Sr/Tb/K/Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgONa/Ga/Gd/Al Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Na/Ga/Gd/Al/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ba/Rh/Ta Ba/Rh/Ta/Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Ba/Ta Ba/Ta/ Ba/Ta/ Ba/Ta/ Ba/Ta/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/Al/Bi Na/Al/Bi/ Na/Al/Bi/ Na/Al/Bi/Na/Al/Bi/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Cs/Eu/S Cs/Eu/S/Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOSm/Tm/Yb/Fe Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sm/Tm/Yb Sm/Tm/Yb/Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Hf/Zr/Ta Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Rb/Gd/Li/K Rb/Gd/Li/K/ Rb/Gd/Li/K/Rb/Gd/Li/K/ Rb/Gd/Li/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOGd/Ho/Al/P Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/Ca/Lu Na/Ca/Lu/Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Cu/Sn Cu/Sn/ Cu/Sn/ Cu/Sn/ Cu/Sn/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ag/Au Ag/Au/ Ag/Au/ Ag/Au/ Ag/Au/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Al/Bi Al/Bi/ Al/Bi/ Al/Bi/Al/Bi/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Al/Mo Al/Mo/ Al/Mo/Al/Mo/ Al/Mo/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Hf/RbSr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Al/Nb Al/Nb/ Al/Nb/ Al/Nb/ Al/Nb/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Au/Pt Au/Pt/ Au/Pt/ Au/Pt/Au/Pt/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ga/Bi Ga/Bi/ Ga/Bi/Ga/Bi/ Ga/Bi/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Mg/W Mg/W/Mg/W/ Mg/W/ Mg/W/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Pb/AuPb/Au/ Pb/Au/ Pb/Au/ Pb/Au/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Sn/Mg Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Zn/Bi Zn/Bi/ Zn/Bi/ Zn/Bi/ Zn/Bi/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Ta Sr/Ta/ Sr/Ta/ Sr/Ta/Sr/Ta/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na Na/ Na/ Na/ Na/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr Sr/ Sr/ Sr/ Sr/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ca Ca/ Ca/ Ca/ Ca/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Yb Yb/ Yb/ Yb/ Yb/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Cs Cs/ Cs/ Cs/ Cs/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sb Sb/ Sb/ Sb/ Sb/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Gd/Ho Gd/Ho/ Gd/Ho/ Gd/Ho/Gd/Ho/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Zr/Bi Zr/Bi/ Zr/Bi/Zr/Bi/ Zr/Bi/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ho/Sr Ho/Sr/Ho/Sr/ Ho/Sr/ Ho/Sr/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/BSr/B/ Sr/B/ Sr/B/ Sr/B/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOGd/Ho/Sr Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ca/Sr Ca/Sr/ Ca/Sr/ Ca/Sr/ Ca/Sr/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ca/Sr/W Ca/Sr/W/ Ca/Sr/W/Ca/Sr/W/ Ca/Sr/W/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgONa/Zr/Eu/Tm Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Ho/Tm/Na Sr/Ho/Tm/Na/Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Pb Sr/Pb/ Sr/Pb/ Sr/Pb/ Sr/Pb/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/W/Li Sr/W/Li/ Sr/W/Li/Sr/W/Li/ Sr/W/Li/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ca/Sr/WCa/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Sr/Hf Sr/Hf/ Sr/Hf/ Sr/Hf/ Sr/Hf/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Au/Re Au/Re/ Au/Re/ Au/Re/ Au/Re/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/W Sr/W/ Sr/W/ Sr/W/Sr/W/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/Nd La/Nd/ La/Nd/La/Nd/ La/Nd/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/Sm La/Sm/La/Sm/ La/Sm/ La/Sm/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/CeLa/Ce/ La/Ce/ La/Ce/ La/Ce/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO La/Sr La/Sr/ La/Sr/ La/Sr/ La/Sr/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/Nd/Sr La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/La/Nd/Sr/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/Bi/SrLa/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/Ce/Nd/Sr La/Ce/Nd/Sr/ La/Ce/Nd/Sr/La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOLa/Bi/Ce/Nd/Sr La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/La/Bi/Ce/Nd/Sr/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Eu/GdEu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Ca/Na Ca/Na/ Ca/Na/ Ca/Na/ Ca/Na/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Eu/Sm Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Eu/Sr Eu/Sr/ Eu/Sr/ Eu/Sr/Eu/Sr/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Mg/Sr Mg/Sr/ Mg/Sr/Mg/Sr/ Mg/Sr/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ce/Mg Ce/Mg/Ce/Mg/ Ce/Mg/ Ce/Mg/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Gd/SmGd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Au/Pb Au/Pb/ Au/Pb/ Au/Pb/ Au/Pb/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Bi/Hf Bi/Hf/ Bi/Hf/ Bi/Hf/ Bi/Hf/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Rb/S Rb/S/ Rb/S/ Rb/S/Rb/S/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Nd Sr/Nd/ Sr/Nd/Sr/Nd/ Sr/Nd/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Eu/Y Eu/Y/Eu/Y/ Eu/Y/ Eu/Y/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Hf/KSr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Mg/Nd Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/Mg La/Mg/ La/Mg/ La/Mg/ La/Mg/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Mg/Nd/Fe Mg/Nd/Fe/Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Rb/Sr Rb/Sr/ Rb/Sr/ Rb/Sr/ Rb/Sr/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO *Ln1 and Ln2 are each independently alanthanide element, wherein Ln1 and Ln2 are not the same and x is anumber ranging from greater than 0 to less than 4

composition represented by E¹/E²/E³ etc., wherein E¹, E² and E³ are eachindependently an element or a compound comprising one or more elements,refers to a nanowire composition comprised of a mixture of E¹, E² andE³. E¹/E²/E³ etc. are not necessarily present in equal amounts and neednot form a bond with one another. For example, a nanowire comprisingLi/MgO refers to a nanowire comprising Li and MgO, for example, Li/MgOmay refer to a MgO nanowire doped with Li. By way of another example, ananowire comprising NaMnO₄/MgO refers to a nanowire comprised of amixture of NaMnO₄ and MgO. Dopants may be added in suitable form. Forexample in a lithium doped magnesium oxide nanowire (Li/MgO), the Lidopant can be incorporated in the form of Li₂O, Li₂CO₃, LiOH, or othersuitable forms. Li may be fully incorporated in the MgO crystal lattice(e.g., (Li,Mg)O) as well. Dopants for other nanowires may beincorporated analogously.

In some more specific embodiments, the dopant is selected from Li, Baand Sr. In other specific embodiments, the nanowires comprise Li/MgO,Ba/MgO, Sr/La₂O₃, Ba/La₂O₃, Mn/Na₂WO₄, Mn₂O₃/Na₂WO₄, Mn₃O₄/Na₂WO₄,Mg₆MnO₈, Li/B/Mg₆MnO₈, Na/B/Mg₆MnO₈, Zr₂Mo₂O₈ or NaMnO₄/MgO.

In some other specific embodiments, the nanowire comprises a mixed oxideof Mn and Mg with or without B and with or without Li. Additionaldopants for such nanowires may comprise doping elements selected fromGroup 1 and 2 and groups 7-13. The dopants may be present as singledopants or in combination with other dopants. In certain specificembodiments of nanowires comprising a mixed oxide of Mn and Mg with orwithout B and with or without Li., the dopant comprises a combination ofelements from group 1 and group 8-11.

Nanowires comprising mixed oxides of Mn and Mg are well suited forincorporation of dopants because magnesium atoms can be easilysubstituted by other atoms as long as their size is comparable withmagnesium. A family of “doped” Mg₆MnO₈ compounds with the compositionM_((x))Mg_((6-x))MnO₈, wherein each M is independently a dopant asdefined herein and x is 0 to 6, can thus be created. The oxidation stateof Mn can be tuned by selecting different amounts (i.e., differentvalues of x) of M with different oxidation states, for exampleLi_((x))Mg_((6-x))MnO₈ would contain a mixture of Mn(IV) and Mn(V) withx<1 and a mixture that may include Mn(V), Mn(VI), Mn(VII) with x>1. Themaximum value of x depends on the ability of a particular atom M to beincorporated in the Mg₆MnO₈ crystal structure and therefore variesdepending on M. It is believed that the ability to tune the manganeseoxidation state as described above could have advantageous effect on thecatalytic activity of the disclosed nanowires.

Examples of nanowires comprising Li/Mn/Mg/B and an additional dopantinclude; Li/Mn/Mg/B doped with Co; Li/Mn/Mg/B doped with Na, Li/Mn/Mg/Bdoped with Be; Li/Mn/Mg/B doped with Al; Li/Mn/Mg/B doped with Hf;Li/Mn/Mg/B doped with Zr; Li/Mn/Mg/B doped with Zn; Li/Mn/Mg/B dopedwith Rh and Li/Mn/Mg/B doped with Ga. Nanowires comprising Li/Mn/Mg/Bdoped with different combinations of these dopants are also provided.For example, in some embodiments the Li/Mn/Mg/B nanowires are doped withNa and Co. In other embodiments, the Li/Mn/Mg/B nanowires are doped withGa and Na.

In other embodiments, nanowires comprising Mn/W with or without dopantsare provided. For example, the present inventors have found through highthroughput testing that nanowires comprising Mn/W and various dopantsare good catalysts in the OCM reaction. Accordingly, in someembodiments, the Mn/W nanowires are doped with Ba. In other embodiments,the Mn/W nanowires are doped with Be. In yet other embodiments, the Mn/Wnanowires are doped with Te.

In any of the above embodiments, the Mn/W nanowires may comprise a SiO₂support. Alternatively, the use of different supports such as ZrO₂, HfO₂and In₂O₃ in any of the above embodiments has been shown to promote OCMactivity at reduced temperature compared to the same catalyst supportedon silica with limited reduction in selectivity.

Nanowires comprising rare earth oxides doped with various elements arealso effective catalysts in the OCM reaction. In certain specificembodiments, the rare earth oxide or oxy-hydroxide can be any rareearth, preferably La, Nd, Eu, Sm, Yb, Gd. In certain embodiments of thenanowires comprising rare earth elements or yttria, the dopant comprisesalkali earth (group 2) elements. The degree of effectiveness of aparticular dopant is a function of the rare earth used and theconcentration of the alkali earth dopant. In addition to Alkali earthelements, further embodiments of the rare earth or yttria nanowiresinclude embodiments wherein the nanowires comprise alkali elements asdopants, which further promote the selectivity of the OCM catalyticactivity of the doped material. In yet other embodiments of theforegoing, the nanowires comprise both an alkali element and alkaliearth element as dopant. In still further embodiments, an additionaldopant can be selected from an additional rare earth and groups 3, 4, 8,9, 10, 13, 14.

The foregoing rare earth catalyst may be doped prior to, or afterformation of the rare earth oxide. In one embodiment, the correspondingrare earth salt is mixed with the corresponding dopant salt to form asolution or a slurry which is dried and then calcined in a range of 400°C. to 900° C., or between 500° C. and 700° C. In another embodiment, therare earth oxide is formed first through calcination of a rare earthsalt and then contacted with a solution comprising the doping elementprior to drying and calcination between 300° C. and 800° C., or between400° C. and 700° C.

In other embodiments, the nanowires comprise La₂O₃ or LaO_(y)(OH)_(x),wherein y ranges from 0 to 1.5, x ranges from 0 to 3 and 2y+x=3, dopedwith Na, Mg, Ca, Sr, Ga, Sc, Y, Zr, In, Nd, Eu, Sm, Ce, Gd orcombinations thereof. In yet further embodiments, the La₂O₃ orLaO_(y)(OH)_(x) nanowires are doped with binary dopant combinations, forexample Eu/Na; Eu/Gd; Ca/Na; Eu/Sm; Eu/Sr; Mg/Sr; Ce/Mg; Gd/Sm, Mg/Na,Mg/Y, Ga/Sr, Nd/Mg, Gd/Na or Sm/Na. In some other embodiments, the La₂O₃or LaO_(y)(OH)_(x) nanowires are doped with a ternary dopantcombination, for example Ca—Mg—Na.

In other embodiments, the nanowires comprise Nd₂O₃ or NdO_(y)(OH)_(x),wherein y ranges from 0 to 1.5, x ranges from 0 to 3 and 2y+x=3, dopedwith Sr, Ca, Rb, Li, Na or combinations thereof. In certain otherembodiments, the Nd₂O₃ or NdO_(y)(OH)_(x) nanowires are doped withbinary dopant combinations, for example Ca/Sr, Rb/Sr, Ta/Sr or Al/Sr.

In still other examples of doped nanowires, the nanowires comprise Yb₂O₃or YbO_(y)(OH)_(x), wherein y ranges from 0 to 1.5, x ranges from 0 to 3and 2y+x=3, doped with Sr, Ca, Ba, Nd or combinations thereof. Incertain other embodiments, the Yb₂O₃ or YbO_(y)(OH)_(x) OCM nanowiresare doped with a binary combination, for example of Sr/Nd.

Still other examples of doped nanowires Eu₂O₃ or EuO_(y)(OH)_(x)nanowires, wherein y ranges from 0 to 1.5, x ranges from 0 to 3 and2y+x=3, doped with Sr, Ba, Sm, Gd, Na or combinations thereof or abinary dopant combination, for example Sr/Na or Sm/Na.

Example of dopants for Sm₂O₃ or SmO_(y)(OH)_(x) nanowires, wherein x andy are each independently an integer from 1 to 10, include Sr, andexamples of dopants for Y₂O₃ or YO_(y)(OH)_(x) nanowires, wherein yranges from 0 to 1.5, x ranges from 0 to 3 and 2y+x=3, comprise Ga, La,Nd or combinations thereof. In certain other embodiments, the Y₂O₃ orYO_(y)(OH)_(x) nanowires comprise a binary dopant combination, forexample Sr/Nd, Eu/Y or Mg/Nd or a tertiary dopant combination, forexample Mg/Nd/Fe.

In yet other embodiments, the nanowires comprise Ln₂O₃ orLn_(z)O_(y)(OH)_(x), wherein Ln is at each occurrence, independently alanthanide, x ranges from 0 to 3 and 2y+x=3, y ranges from 0 to 1.5, andz is 1, 2 or 3, and the nanowires are doped with Li, Na, K, Rb, Cs, Mg,Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb,Lu, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Mn, Ni, Pd, Pt, Cu, Ag, Au, Zn, Al,Ga, In, Tl, Ge, Sn, Pb, P, As, Sb, Bi, S, Se, Te or combinationsthereof. In certain other embodiments, the Ln₂O₃ or Ln_(z)O_(y)(OH)_(x)nanowires comprise only one dopant, for example Sr, a binary dopantcombination, for example Na/Mg, Na/Sr, Mg/Sr, Li/Cs, Sr/W, Hf/Bi, Na/Eu,Zn/K, Sb/Ag, Sr/Ta, a tertiary dopant combination, for example Li/Na/Sr,Na/La/Eu, Li/Sr/Cs, Dy/Rb/Gd, Mg/La/K, or a quaternary dopantcombination, for example Na/Zr/Eu/Ca, Na/La/Eu/In, Na/K/Mg/Tm,Li/Cs/Sr/Tm, Ba/Tm/Zn/K, Mg/La/Yb/Zn.

Rare earth nanowires, which without doping often have low OCMselectivity, can be greatly improved by doping to reduce theircombustion activity. In particular, nanowires comprising CeO₂ and Pr₂O₃tend to have strong total oxidation activity for methane, however dopingwith additional rare earth elements can significantly moderate thecombustion activity and improve the overall utility of the catalyst.Example of dopants for improving the selectivity for Pr₂O₃ orPrO_(y)(OH)_(x) nanowires, wherein y ranges from 0 to 1.5, x ranges from0 to 3 and 2y+x=3, comprise binary dopants, for example Nd/Mg, La/Mg orYb/Sr.

In some embodiments, dopants are present in the nanowires in, forexample, less than 50 at %, less than 25 at %, less than 10 at %, lessthan 5 at % or less than 1 at %.

In other embodiments of the nanowires, the atomic ratio (w/w) of the oneor more metal elements selected from Groups 1-7 and lanthanides andactinides in the form of an oxide and the dopant ranges from 1:1 to10,000:1, 1:1 to 1,000:1 or 1:1 to 500:1.

In further embodiments, the nanowires comprise one or more metalelements from Group 2 in the form of an oxide and a dopant from Group 1.In further embodiments, the nanowires comprise magnesium and lithium. Inother embodiments, the nanowires comprise one or more metal elementsfrom Group 2 and a dopant from Group 2, for example, in someembodiments, the nanowires comprise magnesium oxide and barium. In otherembodiments, the nanowires comprise one or more metal elements fromGroup 2, a dopant from Group 2 and an additional dopant, for example, insome embodiments, the nanowires comprise magnesium oxide and are dopedwith strontium and tungsten dopants (i.e., Sr/W/MgO). In anotherembodiment, the nanowires comprise an element from the lanthanides inthe form of an oxide and a dopant from Group 1 or Group 2. In furtherembodiments, the nanowires comprise lanthanum and strontium.

Various methods for preparing doped nanowires are provided. In oneembodiment, the doped nanowires can be prepared by co-precipitating ananowire metal oxide precursor and a dopant precursor. In theseembodiments, the doping element may be directly incorporated into thenanowire.

Template Directed Synthesis of Nanowires

In some embodiments, the nanowires can be prepared in a solution phaseusing an appropriate template. In this context, an appropriate templatecan be any synthetic or natural material, or combination thereof, thatprovides nucleation sites for binding ions (e.g. metal element ionsand/or hydroxide or other anions) and causing the growth of a nanowire.The templates can be selected such that certain control of thenucleation sites, in terms of their composition, quantity and locationcan be achieved in a statistically significant manner. The templates aretypically linear or anisotropic in shape, thus directing the growth of ananowire.

In contrast to other template directed preparation of nanostructures,the nanowires of the invention are generally not prepared fromnanoparticles deposited on a template in a reduced state which are thenheat treated and fused into an elongated nanoporous nanostructure. Inparticular, such methods are not generally applicable to continuousnanowires comprising one or more elements from any of Groups 1 through7, lanthanides, actinides or combinations thereof. Instead of forming aplurality of catalyst nanoparticles, nanocrystals, or nanocrystalliteson the surface of the template, the nanowires of the invention arepreferably prepared by nucleation of an oxidized metal element (e.g., inthe form of a metal ion) and subsequent growth of a nanowire. Afternucleation of the oxidized metal element, the nanowires are generallycalcined to produce the desired oxide, but annealing of nanoparticles isnot necessary to form the nanowires.

Accordingly, the nanowires used in the context of the invention have anumber of properties that differentiate them from other nanostructures,such as those created as fused aggregates of nanoparticles. Inparticular, the nanowires are characterized as having one or more of; asubstantially non-nanoporous structure, an average crystal domain size,either before and/or after calcination, of greater than 5 nm, and ananisotropic crystal habit.

In the context of non-nanoporous nanowires, preferred compositions aredistinguished from elongated nanostructures formed as nanoporousaggregates of nanoparticles by virtue of their substantiallynon-nanoporous structures. Such substantially non-nanoporous nanowirestructures will preferably have a surface area of less than 150 m²/g,more preferably less than 100 m²/g, less than 50 m²/g, less than 40m²/g, less than 30 m²/g less than 25 m²/g, less than 20 m²/g, less than15 m²/g, less than 10 m²/g, or between 1 m²/g and any of the foregoing.As will be appreciated, nanowires created through templating processes,where additional aggregates may fuse to a non-nanoporous orsubstantially non-nanoporous nanowire core, will typically have highersurface areas, e.g., surface areas toward the higher end of the range,while nanowires created from other processes, e.g., by hydrothermalprocesses, will typically have lower surface areas.

In certain aspects, the nanowires of the invention are characterized byrelatively large crystal domain sizes in the context of relatively highsurface area nanowire structures. In particular, and as notedpreviously, for those nanowires of the invention having an averagecrystal domain size in at least one crystal dimension that is greaterthan 5 nm, preferred nanowires of the invention will typically have anaverage crystal domain size in at least one crystal dimension that isgreater than 10 nm, and in more preferred aspects, greater than 20 nm.

In certain embodiments, the nanowires of the invention may also becharacterized by additional structural properties. For example, incertain aspects, the nanowires of the invention may be characterized bya continuous crystal structure within the nanowire, excluding stackingfaults. In certain aspects, the nanowires of the invention may becharacterized by an aligned crystal structure within the nanowireconsisting of parallel, aligned crystal domains.

In some embodiments, methods for forming nanowires having the empiricalformula M4_(w)M5_(x)M6_(y)O_(z) are provided, wherein M4 comprises oneor more elements selected from Groups 1 through 4, M5 comprises one ormore elements selected from Group 7 and M6 comprises one or moreelements selected from Groups 5 through 8 and Groups 14 through 15 andw, x, y and z are integers such that the overall charge is balanced. Themethods comprise combining one or more sources of M4, one or moresources of M5, and one or more sources of M6 in the presence of atemplating agent and a solvent to form a mixture. In certain embodimentsthe templating agent is a polymer, for example PVP(polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI (polyethyleneimine),PEG (polyethyleneglycol), polyether, polyesters, polyamides, dextran andother sugar polymers, functionalized hydrocarbon polymers,functionalized polystyrene, polylactic acid, polycaprolactone,polyglycolic acid, poly(ethylene glycol)-poly(propyleneglycol)-poly(ethylene glycol), copolymers or combinations thereof.

In certain embodiments, M4 includes one or more elements selected fromGroup 1, such as Na, while M6 includes one or more elements selectedfrom Group 6, such as W and M3 is Mn. In one embodiment, M4 is Na andthe source of M4 is NaCl, M5 is Mn and the source of M5 is Mn(NO₃)₂, M6is W and the source of M6 is WO₃, the solvent is water, and thetemplating agent is a polymer, for example PVP (polyvinlpyrrolidone),PVA (polyvinylalcohol), PEI (polyethyleneimine), PEG(polyethyleneglycol), polyether, polyesters, polyamides, dextran andother sugar polymers, functionalized hydrocarbon polymers,functionalized polystyrene, polylactic acid, polycaprolactone,polyglycolic acid, poly(ethylene glycol)-poly(propyleneglycol)-poly(ethylene glycol), copolymers or combinations thereof.

In various embodiments, the source of M4 can be one or more of achloride, bromide, iodide, oxychloride, oxybromide, oxyiodide, nitrate,oxynitrate, sulfate or phosphate salt of any of Group 1, Group 2, Group3, or a Group 4 element. In an embodiment, sources of M4 include LiCl,KCl, MgCl₂, CaCl₂, ScCl₃, TiCl₄, KBr, CaBr₂, Sc(NO₃)₃, Y(NO₃)₃, TiBr₄,ZrBr₄, Zr(NO₃)₄, ZrOCl₂, ZrO(NO₃)₂, Na₂SO₄, and Zr(SO₄)₂. For any givensource of M4, a source of M6 can be one or more of an oxide, oxide salt,or an oxyacid of any of Group 5, Group 6, Group 7, Group 8, Group 14 andGroup 15 elements. In an embodiment, sources of M6 include MoO₃,(NH₄)₆MO₇O₂₄, WO₃, Na₂WO₄, H₂WO₄, Co₂O₃, P₂O₅, H₃PO₄ and H₂SiO₄. For anygiven combination of a source of M4 and a source of M6, a source of Mncan be, but is not limited to, any chloride, bromide, nitrate, orsulfate of manganese, including MnCl₂, MnCl₃, MnCl₄, Mn(NO₃)₃, MnSO₄ andMn₂(SO₄)₃.

In still other embodiments, the templating agent can include asurfactant, such as tetraoctylammonium chloride, ammonium laurylsulfate, or lauryl glucoside. For any templating agent or any source ofM4, M6, or Mn, the solvent can include an organic solvent, such asethanol, diethyl ether, or acetonitrile. Additionally, any embodiment ofthe method for forming a nanowire described above can include anyadditional component in the reaction mixture, such as a base.

Nanowire-forming methods of various embodiments of the inventioncomprise combining a source of M4, a source of M5, a source of M6, atemplating agent (e.g., polymer), and a solvent in a reaction mixture.In other embodiments, however, nanowire-forming methods of the presentinvention comprise combining two of a source of M4, a source of M5 and asource of M6 in the presence of a templating agent and a solvent to forman intermediate nanowire and then combining a remainder of the source ofM4, the source of M5 and the source of M6 with the intermediatenanowire, wherein M4 includes one or more elements selected from Group1, Group 2, Group 3 and Group 4 elements, wherein M5 includes one ormore elements selected from Group 7, and wherein M6 includes one or moreelements selected from Group 5, Group 6, Group 7, Group 8, Group 14 andGroup 15 elements. In an embodiment, an intermediate nanowire is formedby combining the source of M5 and the source of M6 in the presence ofthe templating agent and the solvent, followed by combining theintermediate nanowire with the source of M4.

1. Polymer Template

As discussed above, the present disclosure provides nanowires andmethods for preparing the same via polymer template methods. Polymer or“soft” templates have extensively been used in materials synthesis toprepare materials with unique nano and microstructures. Polymertemplated materials may have irregular, ordered, or shape specificstructures. To a large extent, the resulting structure is predicated onthe interaction of the polymer and the inorganic material to betemplated. For example, changing the polymer templating agent whileleaving the metal precursor the same can have drastic effects on themetal/metal oxide end structure. The ability to tune the metal/metaloxide structure to achieve a desired catalytic performance has been anongoing goal in the field of catalysis. Thus, the presently disclosedmethods find utility in for preparation of carious catalytic structures,for example nanowires.

Polymers can be used to prepare templated and textured metal oxide OCMcatalysts, for example in the form of nanowires. This inventiondescribes a simple method to prepare metal and mixed metal oxide OCMcatalysts using polymer templates. In one embodiment, the disclosedmethods employ polymers (e.g., water-soluble polymers) with a wide rangeof molecular weights, as the templating source. Exemplary polymersinclude PVP (polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI(polyethyleneimine), PEG (polyethyleneglycol), polyether, polyesters,polyamides, dextran and other sugar polymers, functionalized hydrocarbonpolymers, functionalized polystyrene, polylactic acid, polycaprolactone,polyglycolic acid, poly(ethylene glycol)-poly(propyleneglycol)-poly(ethylene glycol) and copolymers and combinations thereof.In some embodiments, the polymer template is functionalized with atleast one of amine, carboxylic acid, sulfate, alcohol, halogen or thiolgroups. For example the polymer template may be a hydrocarbon orpolystyrene polymer functionalized with at least one of amine,carboxylic acid, sulfate, alcohol halaogen or thiol groups.

Briefly, a metal precursor and polymer are dissolved in water to producea viscous solution. The solution is dried and calcined (oven ormicrowave) to remove the polymer template. In some embodiments, multiplemetal (e.g., M1, M2, etc.) precursors are dissolved in a polymersolution. The solution is dried and calcined as described above to yieldmixed metal oxide systems for OCM catalysis. Another embodiment usesfreeze drying to dry the polymer/metal solution to prepare a morecontrollable porosity in the metal and mixed metal oxide materials.

Some embodiments comprise use of polymers that readily form gels toprepare metal oxides and mixed metal oxides for OCM catalysts. Forexample, agarose readily forms a gel that can be used as a templatingsource by impregnating the gel with metal precursors. One embodiment ofthe present disclosure comprises impregnating a gel (e.g., agarose) withone or more metal precursors to prepare a nanowire comprising one ormore metals, for example a metal oxide or mixed metal oxide. The gel maybe impregnated with multiple metals in one step or via a step wiseimpregnation.

In another embodiment, the disclosed methods comprise treating ametal-polymer gel composite (e.g., agarose) with a base to precipitatethe metal precursors within the gel framework. The precipitated metalsmay then optionally be calcined. Another embodiment uses freeze dryingto remove the water from the metal-polymer gel composite. The agarose isremoved by oven or microwave calcination to yield metal and mixed metalOCM catalysts.

The “Pechini” Method is a convenient method to prepare evenly dispersedmixed metal oxides. The general procedure comprises use of amultifunctional coordinating ligand that chelates to the metal insolution to create a metal coordination complex that can be polymerizedin-situ, using a polyalcohol, to prepare a metal/organic composite.Normally an alpha-hydroxycarboxylic acid, such as citric acid, is usedto form a stable metal complex and can be esterified/cross-linked with apoly-hydroxyalcohol, such as ethylene glycol or glycerol, to form apolymeric resin. Immobilization of the metal complexes in the resinreduces metal segregation and facilitates compositional homogeneity.

2. Nucleation

Nucleation is the process of forming an inorganic nanowire in situ byconverting soluble precursors (e.g., metal salts and anions) intonanocrystals in the presence of a template (e.g., a polymer template).Typically, the nucleation and growth takes place from multiple bindingsites along the length of the polymer template in parallel. The growthcontinues until a structure encasing the polymer template is formed. Insome embodiments this structure is single-crystalline. In otherembodiments the structure is amorphous, and in other embodiments thestructure is polycrystalline. If desired, upon completion of thesynthesis the polymer template can be removed by thermal treatment(˜300° C.) in air or oxygen, without significantly affecting either thestructure or shape of the inorganic material. In addition, dopants canbe either simultaneously incorporated during the growth process or, inanother embodiment, dopants can be incorporated via impregnationtechniques.

(a) Nanowire Growth Methods

FIG. 6 shows a flow chart of a nucleation process for forming a nanowirecomprising a metal oxide. A polymer solution is first prepared (block504), to which metal salt precursor comprising metal ions is added(block 510). Thereafter, an anion precursor is added (block 520). It isnoted that, in various embodiments, the additions of the metal ions andanion precursor can be simultaneous or sequentially in any order. Underappropriate conditions (e.g., pH, molar ratio of the polymer and metalsalt, molar ratio of the metal ions and anions, addition rate, etc.),the metal ions and anions become bound to the polymer, nucleate and growinto a nanowire of M_(m)X_(n)Z_(p) composition (block 524). Followingcalcinations, nanowires comprising M_(m)X_(n) are transformed tonanowires comprising metal oxide (M_(x)O_(y)) (block 530). An optionalstep of doping (block 534) incorporates a dopant (D^(p+)) in thenanowires comprising metal oxide (M_(x)O_(y), wherein x and y are eachindependently a number from 1 to 100. For ease of illustration, FIG. 6depicts calcinations prior to doping; however, in certain embodimentsdoping may be performed prior to calcinations.

Thus, one embodiment provides a method for preparing a nanowirecomprising a metal oxide, a metal oxy-hydroxide, a metal oxycarbonate ora metal carbonate, the method comprising:

a) providing a solution comprising a plurality of polymer templates;

(b) introducing at least one metal ion and at least one anion to thesolution under conditions and for a time sufficient to allow fornucleation and growth of a nanowire comprising a plurality of metalsalts (M_(m)X_(n)Z_(p)) on the template; and

(c) converting the nanowire (M_(m)X_(n)Z_(p)) to a metal oxide nanowirecomprising a plurality of metal oxides (M_(x)O_(y)), metaloxy-hydroxides (M_(x)O_(Y)OH_(z)), metal oxycarbonates(M_(x)O_(y)(CO₃)_(z)), metal carbonate (M_(x)(CO₃)_(y)) or combinationsthereof

wherein:

M is, at each occurrence, independently a metal element from any ofGroups 1 through 7, lanthanides or actinides;

X is, at each occurrence, independently hydroxide, carbonate,bicarbonate, phosphate, hydrogenphosphate, dihydrogenphosphate, sulfate,nitrate or oxalate;

Z is O;

n, m, x and y are each independently a number from 1 to 100; and

p is a number from 0 to 100.

In some embodiments of the foregoing, the polymer template comprises PVP(polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI (polyethyleneimine),PEG (polyethyleneglycol), polyether, polyesters, polyamides, dextran andother sugar polymers, functionalized hydrocarbon polymers,functionalized polystyrene, polylactic acid, polycaprolactone,polyglycolic acid, poly(ethylene glycol)-poly(propyleneglycol)-poly(ethylene glycol), copolymers or combinations thereof. Insome embodiments, the polymer template is functionalized with at leastone of amine, carboxylic acid, sulfate, alcohol, halogen or thiolgroups. For example the polymer template may be a hydrocarbon orpolystyrene polymer functionalized with at least one of amine,carboxylic acid, sulfate, alcohol, halogen or thiol groups.

In some embodiments, the nanowire is dried in an oven, while in otherembodiments the nanowire is freeze dried or air dried. The drying methodmay have an effect on the final morphology, pore size, etc. of theresulting nanowire. Additionally, the solution comprising the polymertemplate may be in the form of a gel and the at least one metal ion isimpregnated therein. The gel may then be dried as described above. Insome embodiments, the metal impregnated gel is treated with a base toprecipitate the metal. In some different embodiments, the polymertemplate is removed from the nanowire by heat treatment or other removalmeans.

In certain other variations of the foregoing, two or more differentmetal ions may be used. This produces nanowires comprising a mixture oftwo or more metal oxides. Such nanowires may be advantageous in certaincatalytic reactions. For example, in some embodiments the nanowirecatalysts may comprise at least a first and second metal oxide whereinthe first metal oxide has better OCM activity than the second metaloxide and the second metal oxide has better ODH activity than the firstmetal oxide. In certain embodiments of the above, Applicants have foundthat it may be advantageous to perform multiple sequential additions ofthe metal ion, This addition technique may be particularly applicable toembodiments wherein two or more different metal ions are employed toform a mixed nanowire (M1M2X_(x)Y_(y), wherein M1 and M2 are differentmetal elements), which can be converted to M1M2O_(z), for example bycalcination. The slow addition may be performed over any period of time,for example from 1 day to 1 week. In this regard, use of a syringe pumpor an automatic (e.g., robotic) liquid dispenser may be advantageous.Slow addition of the components help ensure that they will nucleate onthe polymer template instead of non-selectively precipitate.

In various embodiments, the polymer templates are selected from PVP(polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI (polyethyleneimine),PEG (polyethyleneglycol), polyether, polyesters, polyamides, dextran andother sugar polymers, functionalized hydrocarbon polymers,functionalized polystyrene, polylactic acid, polycaprolactone,polyglycolic acid, poly(ethylene glycol)-poly(propyleneglycol)-poly(ethylene glycol), copolymers or combinations thereof. Insome embodiments, the polymer template is functionalized with at leastone of amine, carboxylic acid, sulfate, alcohol, halogen or thiolgroups. For example the polymer template may be a hydrocarbon orpolystyrene polymer functionalized with at least one of amine,carboxylic acid, sulfate, alcohol, halogen or thiol groups.

In further embodiments, the metal ion is provided by adding one or moremetal salt (as described herein) to the solution. In other embodiments,the anion is provided by adding one or more anion precursor to thesolution. In various embodiments, the metal ion and the anion can beintroduced to the solution simultaneously or sequentially in any order.In some embodiments, the nanowire (M_(m)X_(n)Z_(p)) is converted to ametal oxide nanowire by calcination, which is a thermal treatment thattransforms or decomposes the M_(m)X_(n)Z_(p) nanowire to a metal oxide.In yet another embodiment, the method further comprises doping the metaloxide nanowire with a dopant. Doping may be performed either before orafter calcination. Converting the nanowire to a metal oxide (oroxy-hydroxide, oxy-carbonate, or carbonate, etc.) generally comprisescalcining.

In a variation of the above method, mixed metal oxides can be prepared(as opposed to a mixture of metal oxides). Mixed metal oxides can berepresented by the following formula M1_(w)M2_(x)M3_(y)O_(z), whereinM1, M2 and M3 are each independently absent or a metal element, and w,x, y and z are integers such that the overall charge is balanced. Mixedmetal oxides comprising more than three metals are also contemplated andcan be prepared via an analogous method. Such mixed metal oxides findutility in a variety of the catalytic reactions disclosed herein. Oneexemplary mixed metal oxide is Na₁₀MnW₅O₁₇.

Thus, one embodiment provides a method for preparing a mixed metal oxidenanowire comprising a plurality of mixed metal oxides(M1_(w)M2_(x)M3_(y)O_(z)), the method comprising:

a) providing a solution comprising a plurality of polymer templates;

(b) introducing metal salts comprising M1, M2 and M3 to the solutionunder conditions and for a time sufficient to allow for nucleation andgrowth of a nanowire comprising a plurality of the metal salts on thetemplate; and

(c) converting the nanowire to a mixed metal oxide nanowire comprising aplurality of mixed metal oxides (M1_(w)M2_(x)M3_(y)O_(z)),

wherein:

M1, M2 and M3 are, at each occurrence, independently a metal elementfrom any of Groups 1 through 7, lanthanides or actinides;

n, m, x and y are each independently a number from 1 to 100; and

p is a number from 0 to 100.

In some embodiments of the foregoing, the polymer template comprises PVP(polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI (polyethyleneimine),PEG (polyethyleneglycol), polyether, polyesters, polyamides, dextran andother sugar polymers, functionalized hydrocarbon polymers,functionalized polystyrene, polylactic acid, polycaprolactone,polyglycolic acid, poly(ethylene glycol)-poly(propyleneglycol)-poly(ethylene glycol), copolymers or combinations thereof. Insome embodiments, the polymer template is functionalized with at leastone of amine, carboxylic acid, sulfate, alcohol, halogen or thiolgroups. For example the polymer template may be a hydrocarbon orpolystyrene polymer functionalized with at least one of amine,carboxylic acid, sulfate, alcohol or thiol groups.

In some embodiments, the nanowire is dried in an oven, while in otherembodiments the nanowire is freeze dried or air dried. The drying methodmay have an effect on the final morphology, pore size, etc. of theresulting nanowire. Additionally, the solution comprising the polymertemplate may be in the form of a gel and the at least one metal saltsare impregnated therein. The gel may then be dried as described above.In some embodiments, the metal impregnated gel is treated with a base toprecipitate the metal. In some different embodiments, the polymertemplate is removed from the nanowire by heat treatment or other removalmeans.

In other embodiments, the present disclosure provides a method forpreparing metal oxide nanowires which may not require a calcinationstep. Thus, in some embodiments the method for preparing metal oxidenanowires comprises:

(a) providing a solution that includes a plurality of polymer templates;and

(b) introducing a compound comprising a metal to the solution underconditions and for a time sufficient to allow for nucleation and growthof a nanowire (M_(m)Y_(n)) on the template;

wherein:

M is a metal element from any of Groups 1 through 7, lanthanides oractinides;

Y is O;

n and m are each independently a number from 1 to 100.

In some embodiments of the foregoing, the polymer template comprises PVP(polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI (polyethyleneimine),PEG (polyethyleneglycol), polyether, polyesters, polyamides, dextran andother sugar polymers, functionalized hydrocarbon polymers,functionalized polystyrene, polylactic acid, polycaprolactone,polyglycolic acid, poly(ethylene glycol)-poly(propyleneglycol)-poly(ethylene glycol), copolymers or combinations thereof. Insome embodiments, the polymer template is functionalized with at leastone of amine, carboxylic acid, sulfate, alcohol, halogen or thiolgroups. For example the polymer template may be a hydrocarbon orpolystyrene polymer functionalized with at least one of amine,carboxylic acid, sulfate, alcohol, halogen or thiol groups.

In some embodiments, the nanowire is dried in an oven, while in otherembodiments the nanowire is freeze dried or air dried. The drying methodmay have an effect on the final morphology, pore size, etc. of theresulting nanowire. Additionally, the solution comprising the polymertemplate may be in the form of a gel and the at least one metal isimpregnated therein. The gel may then be dried as described above. Insome embodiments, the metal impregnated gel is treated with a base toprecipitate the metal. In some different embodiments, the polymertemplate is removed from the nanowire by heat treatment or other removalmeans.

In some specific embodiments of the foregoing method, M is an earlytransition metal, for example V, Nb, Ta, Ti, Zr, Hf, W, Mo or Cr. Inother embodiments, the metal oxide is WO₃. In yet another embodiment,the method further comprises doping the metal oxide nanowire with adopant. In some further embodiments, a reagent is added which convertsthe compound comprising a metal into a metal oxide.

In another embodiment the disclosure provides a method for preparing ananowire comprising a metal oxide, a metal oxy-hydroxide, a metaloxycarbonate or a metal carbonate, the method comprises:

a) providing a solution comprising a plurality of a multifunctionalcoordinating ligand;

(b) introducing at least one metal ion to the solution, thereby forminga metal ion-ligand complex;

(c) introducing a polyalcohol to the solution, wherein the polyalcoholpolymerizes with the metal-ion ligand complex to form a polymerizedmetal ion-ligand complex.

In some embodiments, the multifunctional coordinating ligand is analpha-hydroxycarboxylic acid, for example citric acid. In otherembodiments, the polyalcohol is ethylene glycol or glycerol. In yetother embodiments, the method further comprises heating the polymerizedmetal ion-ligand complex to remove substantially all organic material,and optionally heating the remaining inorganic metal to convert it to ametal oxide (i.e., calcine). In another embodiment, nanowires areprepared by using metal salts sensitive to water hydrolysis, for exampleNbCl₅, WCl₆, TiCl₄, ZrCl₄. A polymer template can be placed in ethanolalong with the metal salt. Water is then slowly added to the reaction inorder to convert the metals salts to metal oxide coated template.

By varying the nucleation conditions, including (without limitation):incubation time of polymer and metal salt; incubation time of polymerand anion; concentration of polymer; metal ion concentration, anionconcentration, sequence of adding anion and metal ions; pH; polymercomposition; polymer size; solution temperature in the incubation stepand/or growth step; types of metal precursor salt; types of anionprecursor; addition rate; number of additions; amount of metal saltand/or anion precursor per addition, the time that lapses between theadditions of the metal salt and anion precursor, including, e.g.,simultaneous (zero lapse) or sequential additions followed by respectiveincubation times for the metal salt and the anion precursor, stablenanowires of diverse compositions and surface properties can beprepared. For example, in certain embodiments the pH of the nucleationconditions is at least 7.0, at least 8.0, at least 9.0, at least 10.0,at least 11.0, at least 12.0 or at least 13.0.

As noted above, the rate of addition of reactants (e.g., metal salt,metal oxide, anion precursor, etc.) is one parameter that can becontrolled and varied to produce nanowires having different properties.During the addition of reactants to a solution containing an existingnanowire and/or a templating material, a critical concentration isreached for which the speed of deposition of solids on the existingnanowire and/or templating material matches the rate of addition ofreactants to the reaction mixture. At this point, the concentration ofsoluble cation stabilizes and stops rising. Thus, nanowire growth can becontrolled and maximized by maintaining the speed of addition ofreactants such that near super-saturation concentration of the cation ismaintained. This helps ensure that no undesirable nucleation occurs. Ifsuper-saturation of the anion (e.g., hydroxide) is exceeded, a new solidphase can start nucleating which allows for non-selective solidprecipitation, rather than nanowire growth. Thus, in order toselectively deposit an inorganic layer on an existing nanowire and/or atemplating material, the addition rate of reactants should be controlledto avoid reaching super-saturation of the solution containing thesuspended solids.

Accordingly, in one embodiment, reactant is repeatedly added in smalldoses to slowly build up the concentration of the reactant in thesolution containing the template. In some embodiments, the speed ofaddition of reactant is such that the reactant concentration in thesolution containing the template is near (but less than) the saturationpoint of the reactant. In some other embodiments, the reactant is addedportion wise (i.e., step addition) rather than continuously. In theseembodiments, the amount of reactant in each portion, and the timebetween addition of each portion, is controlled such that the reactantconcentration in the solution containing the template is near (but lessthan) the saturation point of the reactant. In certain embodiments ofthe foregoing, the reactant is a metal cation while in other embodimentsthe reactant is an anion.

Initial formation of nuclei on a template can be obtained by the samemethod described above, wherein the concentration of reactant isincreased until near, but not above, the supersaturation point of thereactant. Such an addition method facilitates nucleation of the solidphase on the template, rather than homogeneous non-seeding nucleation.In some embodiments, it is desirable to use a slower reactant additionspeed during the initial nucleation phase as the super-saturationdepression due to the template might be quite small at this point. Oncethe first layer of solid (i.e., nanowire) is formed on the template, theaddition speed can be increased.

In some embodiments, the addition rate of reactant is controlled suchthat the precipitation rate matches the addition rate of the reactant.In these embodiments, nanowires comprising two or more different metalscan be prepared by controlling the addition rates of two or moredifferent metal cation solutions such that the concentration of eachcation in the templating solution is maintained at or near (but does notexceed) the saturation point for each cation.

In some embodiments, the optimal speed of addition (and step size ifusing step additions) is controlled as a function of temperature. Forexample, in some embodiments the nanowire growth rate is accelerated athigher temperatures. Thus, the addition rate of reactants is adjustedaccording to the temperature of the templating solution.

In other embodiments, modeling (iterative numeric rather than algebraic)of the nanowire growth process is used to determine optimal solutionconcentrations and supernatant re-cycling strategies.

As noted above, the addition rate of reactants can be controlled andmodified to change the properties of the nanowires. In some embodiments,the addition rate of a hydroxide source must be controlled such that thepH of the templating solution is maintained at the desired level. Thismethod may require specialized equipment, and depending on the additionrate, the potential for localized spikes in pH upon addition of thehydroxide source is possible. Thus, in an alternative embodiment thepresent disclosure provides a method wherein the template solutioncomprises a weak base that slowly generates hydroxide in-situ, obviatingthe need for an automated addition sequence.

In the above embodiment, organic epoxides, such as but not limited topropylene oxide and epichlorohydrin, are used to slowly increase thetemplate solution pH without the need for automated pH control. Theepoxides are proton scavengers and undergo an irreversible ring-openingreaction with a nucleophilic anion of the metal oxide precursor (such asbut not limited to Cl⁻ or NO₃ ⁻). The net effect is a slow homogenousraise in pH to form metal hydroxy species in solution that deposit ontothe template surface. In some embodiments, the organic epoxide ispropylene oxide.

An attractive feature of this method is that the organic epoxide can beadded all at once, there is no requirement for subsequent additions oforganic epoxide to grow metal oxide coatings over the course of thereaction. Due to the flexibility of the “epoxide-assisted” coatings, itis anticipated that many various embodiments can be employed to make newtemplated materials (e.g., nanowires). For example, mixed metal oxidenanowires can be prepared by starting with appropriate ratios of metaloxide precursors and propylene oxide in the presence of polymertemplate. In other embodiments, metal oxide deposition on the polymertemplate can be done sequentially to prepare core/shell materials(described in more detail below).

(b) Metal Salt

As noted above, the nanowires are prepared by nucleation of metal ionsin the presence of an appropriate template, for example, a polymer. Inthis respect, any soluble metal salt may be used as the precursor ofmetal ions that nucleate on the template. Soluble metal salts of themetals from Groups 1 through 7, lanthanides and actinides areparticularly useful and all such salts are contemplated.

In one embodiment, the soluble metal salt comprises chlorides, bromides,iodides, nitrates, sulfates, acetates, oxides, oxyhalides, oxynitrates,phosphates (including hydrogenphosphate and dihydrogenphosphate)formates, alkoxides or oxalates of metal elements from Groups 1 through7, lanthanides, actinides or combinations thereof. In more specificembodiments, the soluble metal salt comprises chlorides, nitrates orsulfates of metal elements from Groups 1 through 7, lanthanides,actinides or combinations thereof. The present disclosure contemplatesall possible chloride, bromide, iodide, nitrate, sulfate, acetate,oxide, oxyhalides, oxynitrates, phosphates (including hydrogenphosphateand dihydrogenphosphate) formates, alkoxides and oxalate salts of metalelements from Groups 1 through 7, lanthanides, actinides or combinationsthereof.

In another embodiment, the metal salt comprises LiCl, LiBr, LiI, LiNO₃,Li₂SO₄, LiCO₂CH₃, Li₂C₂O₄, Li₃PO₄, Li₂HPO₄, LiH₂PO₄, LiCO₂H, LiOR, NaCl,NaBr, NaI, NaNO₃, Na₂SO₄, NaCO₂CH₃, Na₂C₂O₄, Na₃PO₄, Na₂HPO₄, NaH₂PO₄,NaCO₂H, NaOR, KCl, KBr, KI, KNO₃, K₂SO₄, KCO₂CH₃, K₂C₂O₄, K₃PO4, K₂HPO₄,KH₂PO₄, KCO₂H, KOR, RbCl, RbBr, RbI, RbNO₃, Rb₂SO₄, RbCO₂CH₃, Rb₂C₂O₄,Rb₃PO₄, Rb₂HPO₄, RbH₂PO₄, RbCO₂H, RbOR, CsCl, CsBr, CsI, CsNO₃, Cs₂SO₄,CsCO₂CH₃, Cs₂C₂O₄, Cs₃PO₄, Cs₂HPO₄, CsH₂PO₄, CsCO₂H, CsOR, BeCl₂, BeBr₂,BeI₂, Be(NO₃)₂, BeSO₄, Be(CO₂CH₃)₂, BeC₂O₄, Be₃(PO4)₂, BeHPO₄,Be(H₂PO₄)₂, Be(CO₂H)₂, Be(OR)₂, MgCl₂, MgBr₂, MgI₂, Mg(NO₃)₂, MgSO₄,Mg(CO₂CH₃)₂, MgC₂O₄, Mg₃(PO₄)₂, MgHPO₄, Mg(H₂PO₄)₂, Mg(CO₂H)₂, Mg(OR)₂,CaCl₂, CaBr₂, CaI₂, Ca(NO₃)₂, CaSO₄, Ca(CO₂CH₃)₂, CaC₂O₄, Mg₃(PO₄)₂,MgHPO₄, Mg(H₂PO₄)₂, Mg(CO₂H)₂, Mg(OR)₂, SrCl₂, SrBr₂, SrI₂, Sr(NO₃)₂,SrSO₄, Sr(CO₂CH₃)₂, SrC₂O₄, Sr₃(PO₄)₂, SrHPO₄, Sr(H₂PO₄)₂, Sr(CO₂H)₂,Sr(OR)₂, BaCl₂, BaBr₂, BaI₂, Ba(NO₃)₂, BaSO₄, Ba(CO₂CH₃)₂, BaC₂O₄,Ba₃(PO₄)₂, BaHPO₄, Ba(H₂PO₄)₂, Ba(CO₂H)₂, Ba(OR)₂, ScCl₃, ScBr₃, ScI₃,Sc(NO₃)₃, Sc₂(SO₄)₃, Sc(CO₂CH₃)₃, Sc₂(C₂O₄)₃, ScPO₄, Sc₂(HPO₄)₃,Sc(H₂PO₄)₃, Sc(CO₂H)₃, Sc(OR)₃, YCl₃, YBr₃, YI₃, Y(NO₃)₃, Y₂(SO₄)₃,Y(CO₂CH₃)₃, Y₂(C₂O₄)₃, YPO₄, Y₂(HPO₄)₃, Y(H₂PO₄)₃, Y(CO₂H)₃, Y(OR)₃,TiCl₄, TiBr₄, TiI₄, Ti(NO₃)₄, Ti(SO₄)₂, Ti(CO₂CH₃)₄, Ti(C₂O₄)₂,Ti₃(PO₄)₄, Ti(HPO₄)₂, Ti(H₂PO₄)₄, Ti(CO₂H)₄, Ti(OR)₄, ZrCl₄, ZrOCl₂,ZrBr₄, ZrI₄, Zr(NO₃)₄, ZrO(NO₃)₂, Zr(SO₄)₂, Zr(CO₂CH₃)₄, Zr(C₂O₄)₂,Zr₃(PO₄)₄, Zr(HPO₄)₂, Zr(H₂PO₄)₄, Zr(CO₂H)₄, Zr(OR)₄, HfCl₄, HfBr₄,HfI₄, Hf(NO₃)₄, Hf(SO₄)₂, Hf(CO₂CH₃)₄, Hf(C₂O₄)₂, Hf₃(PO₄)₄, Hf(HPO₄)₂,Hf(H₂PO₄)₄, Hf(CO₂H)₄, Hf(OR)₄, LaCl₃, LaBr₃, LaI₃, La(NO₃)₃, La₂(SO₄)₃,La(CO₂CH₃)₃, La₂(C₂O₄)₃, LaPO₄, La₂(HPO₄)₃, La(H₂PO₄)₃, La(CO₂H)₃,La(OR)₃, WCl₂, WCl₃, WCl₄, WCl₅, WCl₆, WBr₂, WBr₃, WBr₄, WBr₅, WBr₆,WI₂, WI₃, WI₄, WI₅, WI₆, W(NO₃)₂, W(NO₃)₃, W(NO₃)₄, W(NO₃)₅, W(NO₃)₆,W(CO₂CH₃)₂, W(CO₂CH₃)₃, W(CO₂CH₃)₄, W(CO₂CH₃)₅, W(CO₂CH₃)₆, WC₂O₄,W₂(C₂O₄)₃, W(C₂O₄)₂, W₂(C₂O₄)₅, W(C₂O₄)₆, WPO₄, W₂(HPO₄)₃, W(H₂PO₄)₃,W(CO₂H)₃, W(OR)₃, W₃(PO₄)₄, W(HPO₄)₂, W(H₂PO₄)₄, W(CO₂H)₄, W(OR)₄,W₃(PO₄)₅, W₂(HPO₄)₅, W(H₂PO₄)₅, W(CO₂H)₅, W(OR)₅, W(PO₄)₂, W(HPO₄)₃,W(H₂PO₄)₆, W(CO₂H)₆, W(OR)₆, MnCl₂MnCl₃, MnBr₂MnBr₃, MnI₂MnI₃, Mn(NO₃)₂,Mn(NO₃)₃, MnSO₄, Mn₂(SO₄)₃, Mn(CO₂CH₃)₂, Mn(CO₂CH₃)₃, MnC₂O₄,Mn₂(C₂O₄)₃, Mn₃(PO₄)₂, MnHPO₄, Mn(H₂PO₄)₂, Mn(CO₂H)₂, Mn(OR)₂, MnPO₄,Mn₂(HPO₄)₃, Mn(H₂PO₄)₃, Mn(CO₂H)₃, Mn(OR)₃, MoCl₂, MoCl₃, MoCl₄, MoCl₅,MoBr₂, MoBr₃, MoBr₄, MoBr₅, MoI₂, MoI₃, MoI₄, MoI₅, Mo(NO₃)₂, Mo(NO₃)₃,Mo(NO₃)₄, Mo(NO₃)₅, MoSO₄, Mo₂(SO₄)₃, Mo(SO₄)₂, Mo₂(SO₄)₅, Mo(CO₂CH₃)₂,Mo(CO₂CH₃)₃, Mo(CO₂CH₃)₄, Mo(CO₂CH₃)₅, MoC₂O₄, Mo₂(C₂O₄)₃, Mo(C₂O₄)₂,MO₂(C₂O₄)₅, Mo₃(PO₄)₂, MoHPO₄, Mo(H₂PO₄)₂, Mo(CO₂H)₂, Mo(OR)₂, MoPO₄,MO₂(HPO₄)₃, Mo(H₂PO₄)₃, Mo(CO₂H)₃, Mo(OR)₃, Mo₃(PO₄)₄, Mo(HPO₄)₂,Mo(H₂PO₄)₄, Mo(CO₂H)₄, Mo(OR)₄, Mo₃(PO₄)₅, Mo₂(HPO₄)₅, Mo(H₂PO₄)₅,Mo(CO₂H)₅, Mo(OR)₅, VCl, VCl₂, VCl₃, VCl₄, VCl₅, VBr, VBr₂, VBr₃, VBr₄,VBr₅, VI, VI₂, VI₃, VI₄, VI₅, VNO₃, V(NO₃)₂, V(NO₃)₃, V(NO₃)₄, V(NO₃)₅,V₂SO₄, VSO₄, V₂(SO₄)₃, V(SO₄)₄, VCO₂CH₃, V(CO₂CH₃)₂, V(CO₂CH₃)₃,V(CO₂CH₃)₄, V₂C₂O₄, VC₂O₄, V₂(C₂O₄)₃, V(C₂O₄)₄, V₃PO₄, V₂HPO₄, VH₂PO₄,VCO₂H, VOR, V₃(PO₄)₂, VHPO₄, V(H₂PO₄)₂, V(CO₂H)₂, V(OR)₂, VPO₄,V₂(HPO₄)₃, V(H₂PO₄)₃, V(CO₂H)₃, V(OR)₃, V₃(PO₄)₄, V(HPO₄)₂, V(H₂PO₄)₄,V(CO₂H)₄, V(OR)₄, V₃(PO₄)₅, V₂(HPO₄)₅, V(H₂PO₄)₅, V(CO₂H)₅, V(OR)₅,TaCl, TaCl₂, TaCl₃, TaCl₄, TaCl₅ TaBr, TaBr₂, TaBr₃, TaBr₄, TaBr₅, TaI,TaI₂, TaI₃, TaI₄, TaI₅, TaNO₃, Ta(NO₃)₂, Ta(NO₃)₃, Ta(NO₃)₄, Ta(NO₃)₅,Ta₂SO₄, TaSO₄, Ta₂(SO₄)₃, Ta(SO₄)₄, TaCO₂CH₃, Ta(CO₂CH₃)₂, Ta(CO₂CH₃)₃,Ta(CO₂CH₃)₄, Ta₂C₂O₄, TaC₂O₄, Ta₂(C₂O₄)₃, Ta(C₂O₄)₄, Ta₃PO₄, Ta₂HPO₄,TaH₂PO₄, TaCO₂H, TaOR, Ta₃(PO₄)₂, TaHPO₄, Ta(H₂PO₄)₂, Ta(CO₂H)₂,Ta(OR)₂, TaPO₄, Ta₂(HPO₄)₃, Ta(H₂PO₄)₃, Ta(CO₂H)₃, Ta(OR)₃, Ta₃(PO₄)₄,Ta(HPO₄)₂, Ta(H₂PO₄)₄, Ta(CO₂H)₄, Ta(OR)₄, Ta₃(PO₄)₅, Ta₂(HPO₄)₅,Ta(H₂PO₄)₅, Ta(CO₂H)₅, Ta(OR)₅, NbCl, NbCl₂, NbCl₃, NbCl₄, NbCl₅ NbBr,NbBr₂, NbBr₃, NbBr₄, NbBr₅, NbI, NbI₂, NbI₃, NbI₄, NbI₅, NbNO₃,Nb(NO₃)₂, Nb(NO₃)₃, Nb(NO₃)₄, Nb(NO₃)₅, Nb₂SO₄, NbSO₄, Nb₂(SO₄)₃,Nb(SO₄)₄, NbCO₂CH₃, Nb(CO₂CH₃)₂, Nb(CO₂CH₃)₃, Nb(CO₂CH₃)₄, Nb₂C₂O₄,NbC₂O₄, Nb₂(C₂O₄)₃, Nb(C₂O₄)₄, Nb₃PO₄, Nb₂HPO₄, NbH₂PO₄, NbCO₂H, NbOR,Nb₃(PO₄)₂, NbHPO₄, Nb(H₂PO₄)₂, Nb(CO₂H)₂, Nb(OR)₂, NbPO₄, Nb₂(HPO₄)₃,Nb(H₂PO₄)₃, Nb(CO₂H)₃, Nb(OR)₃, Nb₃(PO₄)₄, Nb(HPO₄)₂, Nb(H₂PO₄)₄,Nb(CO₂H)₄, Nb(OR)₄, Nb₃(PO₄)₅, Nb₂(HPO₄)₅, Nb(H₂PO₄)₅, Nb(CO₂H)₅,Nb(OR)₅, NdCl₃, NdBr₃, NdI₃, Nd(NO₃)₃, Nd₂(SO₄)₃, Nd(CO₂CH₃)₃,Nd₂(C₂O₄)₃, NdPO₄, Nd₂(HPO₄)₃, Nd(H₂PO₄)₃, Nd(CO₂H)₃, Nd(OR)₃, EuCl₃,EuBr₃, EuI₃, Eu(NO₃)₃, Eu₂(SO₄)₃, Eu(CO₂CH₃)₃, Eu₂(C₂O₄)₃, NdPO₄,Nd₂(HPO₄)₃, Nd(H₂PO₄)₃, Nd(CO₂H)₃, Nd(OR)₃, PrCl₃, PrBr₃, PrI₃,Pr(NO₃)₃, Pr₂(SO₄)₃, Pr(CO₂CH₃)₃, Pr₂(C₂O₄)₃, PrPO₄, Pr₂(HPO₄)₃,Pr(H₂PO₄)₃, Pr(CO₂H)₃, Pr(OR)₃, SmCl₃, SmBr₃, SmI₃, Sm(NO₃)₃, Sm₂(SO₄)₃,Sm(CO₂CH₃)₃, Sm₂(C₂O₄)₃, SmPO₄, Sm₂(HPO₄)₃, Sm(H₂PO₄)₃, Sm(CO₂H)₃,Sm(OR)₃, CeCl₃, CeBr₃, CeI₃, Ce(NO₃)₃, Ce₂(SO₄)₃, Ce(CO₂CH₃)₃,Ce₂(C₂O₄)₃CePO₄, Ce₂(HPO₄)₃, Ce(H₂PO₄)₃, Ce(CO₂H)₃, Ce(OR)₃, orcombinations thereof, wherein R is alkyl, alkenyl, alkynyl or aryl.

In more specific embodiments, the metal salt comprises MgCl₂, LaCl₃,ZrCl₄, WCl₄, MoCl₄, MnCl₂MnCl₃, Mg(NO₃)₂, La(NO₃)₃, ZrOCl₂, Mn(NO₃)₂,Mn(NO₃)₃, ZrO(NO₃)₂, Zr(NO₃)₄, or combinations thereof.

In other embodiments, the metal salt comprises NdCl₃, NdBr₃, NdI₃,Nd(NO₃)₃, Nd₂(SO₄)₃, Nd(CO₂CH₃)₃, Nd₂(C₂O₄)₃, EuCl₃, EuBr₃, EuI₃,Eu(NO₃)₃, Eu₂(SO₄)₃, Eu(CO₂CH₃)₃, Eu₂(C₂O₄)₃, PrCl₃, PrBr₃, PrI₃,Pr(NO₃)₃, Pr₂(SO₄)₃, Pr(CO₂CH₃)₃, Pr₂(C₂O₄)₃ or combinations thereof.

In still other embodiments, the metal salt comprises Mg, Ca, Mg, W, La,Nd, Sm, Eu, W, Mn, Zr or mixtures thereof. The salt may be in the formof (oxy)chlorides, (oxy)nitrates or tungstates.

(c) Anion Precursor

The anions, or counter ions of the metal ions that nucleate on thetemplate, are provided in the form of an anion precursor. The anionprecursor dissociates in the solution phase and releases an anion. Thus,the anion precursor can be any stable soluble salts having the desiredanion. For instance, bases such as alkali metal hydroxides (e.g., sodiumhydroxide, lithium hydroxide, potassium hydroxides) and ammoniumhydroxide are anion precursors that provide hydroxide ions fornucleation. Alkali metal carbonates (e.g., sodium carbonate, potassiumcarbonates) and ammonium carbonate are anion precursors that providecarbonates ions for nucleation.

In certain embodiments, the anion precursor comprises one or more metalhydroxide, metal carbonate, metal bicarbonate, metal sulfate, metalphosphate or metal oxalate. Preferably, the metal is an alkali or analkaline earth metal. Thus, the anion precursor may comprise any one ofalkali metal hydroxides, carbonates, bicarbonates, sulfates, phosphatesor oxalate; or any one of alkaline earth metal hydroxides, carbonates,bicarbonates, sulfates, phosphates or oxalates.

In some specific embodiments, the one or more anion precursors compriseLiOH, NaOH, KOH, Sr(OH)₂, Ba(OH)₂, Na₂CO₃, K₂CO₃, NaHCO₃,KHCO₃(NR₄)₂CO₃, and NR₄OH, wherein each R is independently selected fromH, C₁-C₁₈ alkyl, C₁-C₁₈ alkenyl, C₁-C₁₈ alkynyl and C₁-C₁₈ aryl.Ammonium salts may provide certain advantages in that there is lesspossibility of introducing unwanted metal impurities. Accordingly, in afurther embodiment, the anion precursor comprises ammonium hydroxide orammonium carbonate.

The dimensions of the nanowires are comparable to those of the polymertemplates, although they can have different aspect ratios as longergrowth can be used to increase the diameter while the length willincrease in size at a much slower rate. The spacing of monomers on thepolymer surface controls the nucleation location and the catalyticnanowire size based on steric hindrance. The monomer identity can (ormay) dictate the identity, size, shape and crystalline face of thecatalytic nanowire being nucleated. To achieve the desired stochiometrybetween metal elements, support and dopants, polymers comprisingmultiple monomers specific for these discrete materials can be used.Alternatively, precursor salts for the materials can be combined in thereaction at the desired stochiometry

3. Core/Shell Structures

In certain embodiments, nanowires can be grown on a support nanowirethat has no or a different catalytic property. FIG. 7 shows an exemplaryprocess 600 for growing a core/shell nanowire structure. Similar to theprocess described in FIG. 7, a polymer solution is prepared (block 604),to which a first metal salt and a first anion precursor are sequentiallyadded (blocks 610 and 620) in appropriate conditions to allow for thenucleation and growth of a nanowire (M1_(m1)X1_(n1)Z_(p1)) on thepolymer (block 624). Thereafter, a second metal salt and a second anionprecursor are sequentially added (blocks 630 and 634), under conditionsto cause the nucleation and growth of a coating of M2_(m2)X2_(n2)Z_(p2)on the nanowire M1_(m1)X1_(n1)Z_(p1) (block 640). Followingcalcinations, nanowires of a core/shell structureM1_(x1)O_(y1)/M2_(x2)O_(y2) are formed, wherein x1, y1, x2 and y2 areeach independently a number from 1 to 100, and p1 and p2 are eachindependently a number from 0 to 100 (block 644). A further step ofimpregnation (block 650) produces a nanowire comprising a dopant andcomprising a core of M1_(x1)O_(y1) coated with a shell of M2_(x2)O_(y2).For ease of illustration, FIG. 7 depicts calcinations prior to doping;however, in certain embodiments doping may be performed prior tocalcinations. In some embodiments, M1 is Mg, Al, Ga, Ca or Zr. Incertain embodiments of the foregoing, M1 is Mn and M2 is Mg. In otherembodiments, M1 is Mg and M2 is Mn. In other embodiments, M1 is La andM2 is Mg, Ca, Sr, Ba, Zr, Nd, Y, Yb, Eu, Sm or Ce. In other embodiments,M1 is Mg and M2 is La or Nd.

In other embodiments, M1_(x1)O_(y1) comprises La₂O₃ while in otherembodiments M2_(x2)O_(y2) comprises La₂O₃. In other embodiments of theforegoing, M1_(x1)O_(y1) or M2_(x2)O_(y2) further comprises a dopant,wherein the dopant comprises Nd, Mn, Fe, Zr, Sr, Ba, Y or combinationsthereof. Other specific combinations of core/shell nanowires are alsoenvisioned within the scope of the present disclosure.

Thus, one embodiment provides a method for preparing metal oxide, metaloxy-hydroxide, metal oxycarbonate or metal carbonate nanowires in acore/shell structure, the method comprising:

(a) providing a solution that includes a plurality of polymer templates;

(b) introducing a first metal ion and a first anion to the solutionunder conditions and for a time sufficient to allow for nucleation andgrowth of a first nanowire (M1_(m1)X1_(n1)Z_(p1)) on the template; and

(c) introducing a second metal ion and optionally a second anion to thesolution under conditions and for a time sufficient to allow fornucleation and growth of a second nanowire (M2_(m2)X2_(n2)Z_(p2)) on thefirst nanowire (M1_(m1)X1_(n1)Z_(p1));

(d) converting the first nanowire (M1_(m1)X1_(n1)Z_(p1)) and the secondnanowire (M2_(m2)X2_(n2)Z₂) to the respective metal oxide nanowires(M1_(x1)O_(y1)) and (M2_(x2)O_(y2)), the respective metal oxy-hydroxidenanowires (M1_(x1)O_(y1)OH_(z1)) and (M2_(x2)O_(y2)OH_(z2)) therespective metal oxycarbonate nanowires (M1_(x1)O_(y1)(CO₃)_(z1)) and(M2_(x2)O_(y2)(CO₃)_(z2)) or the respective metal carbonate nanowires(M1_(x1)(CO₃)_(y1)) and (M2_(x2)(CO₃)_(y2)),

wherein:

M1 and M2 are the same or different and independently selected from ametal element;

X1 and X2 are the same or different and independently hydroxides,carbonates, bicarbonates, phosphates, hydrogenphosphates,dihydrogenphosphates, sulfates, nitrates or oxalates;

Z is O;

n1, m1, n2, m2, x1, y1, z1, x2, y2 and z2 are each independently anumber from 1 to 100; and

p1 and p2 are independently a number from 0 to 100.

In some embodiments, M1 and M2 are the same or different andindependently selected from a metal element from any of Groups 2 through7, lanthanides or actinides

In various embodiments, the polymer templates are are selected from PVP(polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI (polyethyleneimine),PEG (polyethyleneglycol), polyether, polyesters, polyamides, dextran andother sugar polymers, functionalized hydrocarbon polymers,functionalized polystyrene, polylactic acid, polycaprolactone,polyglycolic acid, poly(ethylene glycol)-poly(propyleneglycol)-poly(ethylene glycol) and copolymers and combinations thereof.In some embodiments, the polymer template is functionalized with atleast one of amine, carboxylic acid, sulfate, alcohol, halogen or thiolgroups. For example the polymer template may be a hydrocarbon orpolystyrene polymer functionalized with at least one of amine,carboxylic acid, sulfate, alcohol, halogen or thiol groups.

In some embodiments, the nanowire is dried in an oven, while in otherembodiments the nanowire is freeze dried or air dried. The drying methodmay have an effect on the final morphology, pore size, etc. of theresulting nanowire. Additionally, the solution comprising the polymertemplate may be in the form of a gel and the metal ions are impregnatedtherein. The gel may then be dried as described above. In some differentembodiments, the polymer template is removed from the nanowire by heattreatment or other removal means.

In further embodiments, the respective metal ion is provided by addingone or more respective metal salts (as described herein) to thesolution. In other embodiments, the respective anions are provided byadding one or more respective anion precursors to the solution. Invarious embodiments, the first metal ion and the first anion can beintroduced to the solution simultaneously or sequentially in any order.Similarly, the second metal ion and optionally the second anion can beintroduced to the solution simultaneously or sequentially in any order.The first and second nanowire are typically converted to a metal oxide,metal oxy-hydroxide, metal oxycarbonate or metal carbonate nanowire in acore/shell structure by calcination.

In yet another embodiment, the method further comprises doping the metaloxide nanowire in a core/shell structure with a dopant.

By varying the nucleation conditions, including the pH of the solution,relative ratio of metal salt precursors and the anion precursors,relative ratios of the precursors and the polymer of the syntheticmixture, stable nanowires of diverse compositions and surface propertiescan be prepared.

In certain embodiments, the core nanowire (the first nanowire) is notcatalytically active or less so than the shell nanowire (the secondnanowire), and the core nanowire serve as an intrinsic catalytic supportfor the more active shell nanowire. For example, ZrO₂ may not have highcatalytic activity in an OCM reaction, whereas Sr²⁺ doped La₂O₃ does. AZrO₂ core thus may serve as a support for the catalytic Sr²⁺ doped La₂O₃shell.

In some embodiments, the present disclosure provides a nanowirecomprising a core/shell structure and comprising a ratio of effectivelength to actual length of less than one. In other embodiments, thenanowires having a core/shell structure comprise a ratio of effectivelength to actual length equal to one.

4. Diversity

As noted above, in some embodiments, the disclosed template-directedsynthesis provides nanowires having diverse compositions and/ormorphologies. This method enables production of a library of nanowirecatalysts with a new level of control over materials composition,materials surface and crystal structure. These nanowires prepared bypolymer-templated methods take advantage of the large variation ofdifferent polymer structures and sizes, etc. to enable combinatorialsynthesis of robust, active and selective inorganic catalyticpolycrystalline nanowires. Modification of the various syntheticparameters permits simultaneous optimization of the nanowires' catalyticproperties in a high-dimensional space.

In various embodiments, the synthetic parameters for nucleating andgrowing nanowires can be manipulated to create nanowires of diversecompositions and morphologies. Typical synthetic parameters include,without limitation, concentration ratios of metal ions and activefunctional groups on the polymer (e.g., various monomers); concentrationratios of metal and anions (e.g., hydroxide); incubation time of polymerand metal salt; incubation time of polymer and anion; concentration ofpolymer; sequence of adding anion and metal ions; pH; polymercomposition and size; solution temperature in the incubation step and/orgrowth step; types of metal precursor salt; types of anion precursor;addition rate, number of additions; the time that lapses between theadditions of the metal salt and anion precursor, including, e.g.,simultaneous (zero lapse) or sequential additions followed by respectiveincubation times for the metal salt and the anion precursor.

Additional variable synthetic parameters include, growth time once bothmetal and anion are present in the solution; choice of solvents(although water is typically used, certain amounts of alcohol, such asmethanol, ethanol and propanol, can be mixed with water); choice and thenumber of metal salts used (e.g., both LaCl₃ and La(NO₃)₃ can be used toprovide La³⁺ ions); choice and the number of anion precursors used(e.g., both NaOH then LiOH can be used to provide the hydroxide); choiceor the number of different polymers used; the presence or absence of abuffer solution; the different stages of the growing step (e.g.,nanowires may be precipitated and cleaned and resuspended in a secondsolution and perform a second growth of the same material (thicker core)or different material to form a core/shell structure.

Thus, libraries of nanowires can be generated with diverse physicalproperties and characteristics such as: composition, e.g., basic metaloxides (M_(x)O_(y)), size, shape, surface morphology, exposed crystalfaces/edge density, crystallinity, dispersion, and stoichiometry andnanowire template physical characteristics including length, width,porosity and pore density. High throughput, combinatorial screeningmethods are then applied to evaluate the catalytic performancecharacteristics of the nanowires (see, e.g., FIG. 2). Based on theseresults, lead target candidates are identified. From these lead targets,further rational modifications to the synthetic designs can be made tocreate nanowires that satisfy certain catalytic performance criteria.This results in further refinement of the nanowire design and materialstructure.

Catalytic Reactions

The present disclosure provides for the use of catalytic nanowires ascatalysts in catalytic reactions and related methods. In someembodiments, the catalytic reaction is any of the reactions describedherein. The morphology and composition of the catalytic nanowires is notlimited, and the nanowires may be prepared by any method. For examplethe nanowires may have a bent morphology or a straight morphology andmay have any molecular composition. In some embodiments, the nanowireshave better catalytic properties than a corresponding bulk catalyst(i.e., a catalyst having the same chemical composition as the nanowire,but prepared from bulk material). In some embodiments, the nanowirehaving better catalytic properties than a corresponding bulk catalysthas a ratio of effective length to actual length equal to one. In otherembodiments, the nanowire having better catalytic properties than acorresponding bulk catalyst has a ratio of effective length to actuallength of less than one. In other embodiments, the nanowire havingbetter catalytic properties than a corresponding bulk catalyst comprisesone or more elements from Groups 1 through 7, lanthanides or actinides.

Nanowires may be useful in any number of reactions catalyzed by aheterogeneous catalyst. Examples of reactions wherein nanowires havingcatalytic activity may be employed are disclosed in Farrauto andBartholomew, “Fundamentals of Industrial Catalytic Processes” BlackieAcademic and Professional, first edition, 1997, which is herebyincorporated in its entirety. Other non-limiting examples of reactionswherein nanowires having catalytic activity may be employed include: theoxidative coupling of methane (OCM) to ethane and ethylene; oxidativedehydrogenation (ODH) of alkanes to the corresponding alkenes, forexample oxidative dehydrogenation of ethane or propane to ethylene orpropylene, respectively; selective oxidation of alkanes, alkenes, andalkynes; oxidation of CO, dry reforming of methane, selective oxidationof aromatics; Fischer-Tropsch, hydrocarbon cracking; combustion ofhydrocarbons and the like. Reactions catalyzed by the disclosednanowires are discussed in more detail below.

The nanowires are generally useful as catalysts in methods forconverting a first carbon-containing compound (e.g., a hydrocarbon, COor CO₂) to a second carbon-containing compound. In some embodiments themethods comprise contacting a nanowire, or material comprising the same,with a gas comprising a first carbon-containing compound and an oxidantto produce a carbon-containing compound. In some embodiments, the firstcarbon-containing compound is a hydrocarbon, CO, CO₂, methane, ethane,propane, hexane, cyclohexane, octane or combinations thereof. In otherembodiments, the second carbon-containing compound is a hydrocarbon, CO,CO₂, ethane, ethylene, propane, propylene, hexane, hexene, cyclohexane,cyclohexene, bicyclohexane, octane, octene or hexadecane. In someembodiments, the oxidant is oxygen, ozone, nitrous oxide, nitric oxide,carbon dioxide, water or combinations thereof.

In other embodiments of the foregoing, the method for conversion of afirst carbon-containing compound to a second carbon-containing compoundis performed at a temperature below 100° C., below 200° C., below 300°C., below 400° C., below 500° C., below 600° C., below 700° C., below800° C., below 900° C. or below 1000° C. In other embodiments, themethod for conversion of a first carbon-containing compound to a secondcarbon-containing compound is performed at a pressure above 0.5 ATM,above 1 ATM, above 2 ATM, above 5 ATM, above 10 ATM, above 25 ATM orabove 50 ATM.

The catalytic reactions described herein can be performed using standardlaboratory equipment known to those of skill in the art, for example asdescribed in U.S. Pat. No. 6,350,716, which is incorporated herein inits entirety.

As noted above, the nanowires disclosed herein have better catalyticactivity than a corresponding bulk catalyst. In some embodiments, theselectivity, yield, conversion, or combinations thereof, of a reactioncatalyzed by the nanowires is better than the selectivity, yield,conversion, or combinations thereof, of the same reaction catalyzed by acorresponding bulk catalyst under the same conditions. For example, insome embodiments, the nanowire possesses a catalytic activity such thatconversion of reactant to product in a reaction catalyzed by thenanowire is greater than at least 1.1 times, greater than at least 1.25times, greater than at least 1.5 times, greater than at least 2.0 times,greater than at least 3.0 times or greater than at least 4.0 times theconversion of reactant to product in the same reaction catalyzed by acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire.

In other embodiments, the nanowire possesses a catalytic activity suchthat selectivity for product in a reaction catalyzed by the nanowire isgreater than at least 1.1 times, greater than at least 1.25 times,greater than at least 1.5 times, greater than at least 2.0 times,greater than at least 3.0 times, or greater than at least 4.0 times theselectivity for product in the same reaction under the same conditionsbut catalyzed by a catalyst prepared from bulk material having the samechemical composition as the nanowire.

In yet other embodiments, the nanowire possesses a catalytic activitysuch that yield of product in a reaction catalyzed by the nanowire isgreater than at least 1.1 times, greater than at least 1.25 times,greater than at least 1.5 times, greater than at least 2.0 times,greater than at least 3.0 times, or greater than at least 4.0 times theyield of product in the same reaction under the same conditions butcatalyzed by a catalyst prepared from bulk material having the samechemical composition as the nanowire.

In yet other embodiments, the nanowire possesses a catalytic activitysuch that activation temperature of a reaction catalyzed by the nanowireis at least 25° C. lower, at least 50° C. lower, at least 75° C. lower,or at least 100° C. lower than the temperature of the same reactionunder the same conditions but catalyzed by a catalyst prepared from bulkmaterial having the same chemical composition as the nanowire.

In certain reactions (e.g., OCM), production of unwanted oxides ofcarbon (e.g., CO and CO₂) is a problem that reduces overall yield ofdesired product and results in an environmental liability. Accordingly,in one embodiment the present disclosure addresses this problem andprovides nanowires with a catalytic activity such that the selectivityfor CO and/or CO₂ in a reaction catalyzed by the nanowires is less thanthe selectivity for CO and/or CO₂ in the same reaction under the sameconditions but catalyzed by a corresponding bulk catalyst. Accordingly,in one embodiment, the present disclosure provides a nanowire whichpossesses a catalytic activity such that selectivity for CO_(x), whereinx is 1 or 2, in a reaction catalyzed by the nanowire is less than atleast 0.9 times, less than at least 0.8 times, less than at least 0.5times, less than at least 0.2 times or less than at least 0.1 times theselectivity for CO_(x) in the same reaction under the same conditionsbut catalyzed by a catalyst prepared from bulk material having the samechemical composition as the nanowire.

In some embodiments, the absolute selectivity, yield, conversion, orcombinations thereof, of a reaction catalyzed by the nanowires disclosedherein is better than the absolute selectivity, yield, conversion, orcombinations thereof, of the same reaction under the same conditions butcatalyzed by a corresponding bulk catalyst. For example, in someembodiments the yield of product in a reaction catalyzed by thenanowires is greater than 20%, greater than 30%, greater than 50%,greater than 75%, or greater than 90%. In other embodiments, theselectivity for product in a reaction catalyzed by the nanowires isgreater than 20%, greater than 30%, greater than 50%, greater than 75%,or greater than 90%. In other embodiments, the conversion of reactant toproduct in a reaction catalyzed by the nanowires is greater than 20%,greater than 30%, greater than 50%, greater than 75%, or greater than90%.

In addition to the improved catalytic performance of the disclosednanowires, the morphology of the nanowires is expected to provide forimproved mixing properties for the nanowires compared to standardcolloidal (e.g., bulk) catalyst materials. The improved mixingproperties are expected to improve the performance of any number ofcatalytic reactions, for example, in the area of transformation of heavyhydrocarbons where transport and mixing phenomena are known to influencethe catalytic activity. In other reactions, the shape of the nanowiresis expected to provide for good blending, reduce settling, and providefor facile separation of any solid material.

In some other chemical reactions, the nanowires are useful forabsorption and/or incorporation of a reactant used in chemical looping.For example, the nanowires find utility as NO_(x) traps, in unmixedcombustion schemes, as oxygen storage materials, as CO₂ sorptionmaterials (e.g., cyclic reforming with high H₂ output) and in schemesfor conversion of water to H₂.

1. Oxidative Coupling of Methane (OCM)

As noted above, the present disclosure provides nanowires havingcatalytic activity and related approaches to nanowire design andpreparation for improving the yield, selectivity and/or conversion ofany number of catalyzed reactions, including the OCM reaction. Asmentioned above, there exists a tremendous need for catalyst technologycapable of addressing the conversion of methane into high valuechemicals (e.g., ethylene and products prepared therefrom) using adirect route that does not go through syngas. Accomplishing this taskwill dramatically impact and redefine a non-petroleum based pathway forfeedstock manufacturing and liquid fuel production yielding reductionsin GHG emissions, as well as providing new fuel sources.

Ethylene has the largest carbon footprint compared to all industrialchemical products in part due to the large total volume consumed into awide range of downstream important industrial products includingplastics, surfactants and pharmaceuticals. In 2008, worldwide ethyleneproduction exceeded 120 M metric tons while growing at a robust rate of4% per year. The United States represents the largest single producer at28% of the world capacity. Ethylene is primarily manufactured from hightemperature cracking of naphtha (e.g., oil) or ethane that is separatedfrom natural gas. The true measurement of the carbon footprint can bedifficult as it depends on factors such as the feedstock and theallocation as several products are made and separated during the sameprocess. However, some general estimates can be made based on publisheddata.

Cracking consumes a significant portion (about 65%) of the total energyused in ethylene production and the remainder is for separations usinglow temperature distillation and compression. The total tons of CO₂emission per ton of ethylene are estimated at between 0.9 to 1.2 fromethane cracking and 1 to 2 from naphtha cracking. Roughly, 60% ofethylene produced is from naphtha, 35% from ethane and 5% from otherssources (Ren, T.; Patel, M. Res. Conserv. Recycl. 53:513, 2009).Therefore, based on median averages, an estimated amount of CO₂emissions from the cracking process is 114M tons per year (based on 120Mtons produced). Separations would then account for an additional 61 Mtons CO₂ per year.

Nanowires provide an alternative to the need for the energy intensivecracking step. Additionally, because of the high selectivity of thenanowires, downstream separations are dramatically simplified, ascompared to cracking which yields a wide range of hydrocarbon products.The reaction is also exothermic so it can proceed via an autothermalprocess mechanism. Overall, it is estimated that up to a potential 75%reduction in CO₂ emission compared to conventional methods could beachieved. This would equate to a reduction of one billion tons of CO₂over a ten-year period and would save over 1M barrels of oil per day.

The nanowires also permit converting ethylene into liquid fuels such asgasoline or diesel, given ethylene's high reactivity and numerouspublications demonstrating high yield reactions, in the lab setting,from ethylene to gasoline and diesel. On a life cycle basis from well towheel, recent analysis of methane to liquid (MTL) using F-T processderived gasoline and diesel fuels has shown an emission profileapproximately 20% greater to that of petroleum based production (basedon a worst case scenario) (Jaramillo, P., Griffin, M., Matthews, S.,Env. Sci. Tech 42:7559, 2008). In the model, the CO₂ contribution fromplant energy was a dominating factor at 60%. Thus, replacement of thecracking and F-T process would be expected to provide a notablereduction in net emissions, and could be produced at lower CO₂ emissionsthan petroleum based production.

Furthermore, a considerable portion of natural gas is found in regionsthat are remote from markets or pipelines. Most of this gas is flared,re-circulated back into oil reservoirs, or vented given its low economicvalue. The World Bank estimates flaring adds 400M metric tons of CO₂ tothe atmosphere each year as well as contributing to methane emissions.The nanowires of this disclosure also provide economic and environmentalincentive to stop flaring. Also, the conversion of methane to fuel hasseveral environmental advantages over petroleum-derived fuel. Naturalgas is the cleanest of all fossil fuels, and it does not contain anumber of impurities such as mercury and other heavy metals found inoil. Additionally, contaminants including sulfur are also easilyseparated from the initial natural gas stream. The resulting fuels burnmuch cleaner with no measurable toxic pollutants and provide loweremissions than conventional diesel and gasoline in use today.

In view of its wide range of applications, the nanowires of thisdisclosure can be used to not only selectively activate alkanes, butalso to activate other classes of inert unreactive bonds, such as C—F,C—Cl or C—O bonds. This has importance, for example, in the destructionof man-made environmental toxins such as CFCs, PCBs, dioxins and otherpollutants. Accordingly, while the invention is described in greaterdetail below in the context of the OCM reaction and other the otherreactions described herein, the nanowire catalysts are not in any waylimited to this particular reaction.

The selective, catalytic oxidative coupling of methane to ethylene (i.e.the OCM reaction) is shown by the following reaction (1):

2CH₄+O₂→CH₂CH₂+2H₂O  (1)

This reaction is exothermic (Heat of Reaction−67 kcals/mole) and usuallyoccurs at very high temperatures (>700° C.). During this reaction, it isbelieved that the methane (CH₄) is first oxidatively coupled into ethane(C₂H₆), and subsequently the ethane (C₂H₆) is oxidatively dehydrogenatedinto ethylene (C₂H₄). Because of the high temperatures used in thereaction, it has been suggested that the ethane is produced mainly bythe coupling in the gas phase of the surface-generated methyl (CH₃)radicals. Reactive metal oxides (oxygen type ions) are apparentlyrequired for the activation of CH₄ to produce the CH₃ radicals. Theyield of C₂H₄ and C₂H₆ is limited by further reactions in the gas phaseand to some extent on the catalyst surface. A few of the possiblereactions that occur during the oxidation of methane are shown below asreactions (2) through (8):

CH₄→CH₃ radical  (2)

CH₃ radical→C₂H₆  (3)

CH₃ radical+2.5O₂→CO₂+1.5H₂O  (4)

C₂H₆→C₂H₄+H₂  (5)

C₂H₆+0.5O₂→C₂H₄+H₂O  (6)

C₂H₄+3O₂→2CO₂+2H₂O  (7)

CH₃ radical+C_(x)H_(y)+O₂→Higher HC's−Oxidation/CO₂+H₂O  (8)

With conventional heterogeneous catalysts and reactor systems, thereported performance is generally limited to <25% CH₄ conversion at <80%combined C₂ selectivity, with the performance characteristics of highselectivity at low conversion, or the low selectivity at highconversion. In contrast, the nanowires of this disclosure are highlyactive and can optionally operate at a much lower temperature. In oneembodiment, the nanowires disclosed herein enable efficient conversionof methane to ethylene in the OCM reaction at temperatures less thanwhen the corresponding bulk material is used as a catalyst. For example,in one embodiment, the nanowires disclosed herein enable efficientconversion (i.e., high yield, conversion, and/or selectivity) of methaneto ethylene at temperatures of less than 900° C., less than 800° C.,less than 700° C., less than 600° C., or less than 500° C. In otherembodiments, the use of staged oxygen addition, designed heatmanagement, rapid quench and/or advanced separations may also beemployed.

Accordingly, one embodiment of the present disclosure is a method forthe preparation of ethan and/or ethylene, the method comprisingconverting methane to ethan and/or ethylene in the presence of acatalytic material, wherein the catalytic material comprises at leastone catalytic nanowire as disclosed herein.

Accordingly, in one embodiment a stable, very active, high surface area,multifunctional nanowire catalyst is disclosed having active sites thatare isolated and precisely engineered with the catalytically activemetal centers/sites in the desired proximity (see, e.g., FIG. 1).

The exothermic heats of reaction (free energy) follow the order ofreactions depicted above and, because of the proximity of the activesites, will mechanistically favor ethylene formation while minimizingcomplete oxidation reactions that form CO and CO₂. Representativenanowire compositions useful for the OCM reaction include, but are notlimited to: highly basic oxides selected from the early members of theLanthanide oxide series; Group 1 or 2 ions supported on basic oxides,such as Li/MgO, Ba/MgO and Sr/La₂O₃; and single or mixed transitionmetal oxides, such as VO_(X) and Re/Ru that may also contain Group 1ions. Other nanowire compositions useful for the OCM reaction compriseany of the compositions disclosed herein, for example MgO, La₂O₃,Na₂WO₄, Mn₂O₃, Mn₃O₄, Mg₆MnO₈, Zr₂Mo₂O₈, NaMnO₄, Mn₂O₃/Na₂WO₄,Mn₃O₄/Na₂WO₄ or Na/MnO₄/MgO, Mn/WO4, Nd₂O₃, Sm₂O₃, Eu₂O₃ or combinationsthereof. Activating promoters (i.e., dopants), such as chlorides,nitrates and sulfates, or any of the dopants described above may also beemployed.

As noted above, the presently disclosed nanowires comprise a catalyticperformance better than corresponding bulk catalysts, for example in oneembodiment the catalytic performance of the nanowires in the OCMreaction is better than the catalytic performance of a correspondingbulk catalyst. In this regard, various performance criteria may definethe “catalytic performance” of the catalysts in the OCM (and otherreactions). In one embodiment, catalytic performance is defined by C2selectivity in the OCM reaction, and the C2 selectivity of the nanowiresin the OCM reactionis >5%, >10%, >15%, >20%, >25%, >30%, >35%, >40%, >45%, >50%, >55%, >60%, >65%, >70%, >75%or >80%.

Other important performance parameters used to measure the nanowires'catalytic performace in the OCM reaction are selected from single passmethane conversion percentage (i.e., the percent of methane converted ona single pass over the catalyst or catalytic bed, etc.), reaction inletgas temperature, reaction operating temperature, total reactionpressure, methane partial pressure, gas-hour space velocity (GHSV), O₂source, catalyst stability and ethylene to ethane ratio. In certainembodiments, improved catalytic performance is defined in terms of thenanowires' improved performance (relative to a corresponding bulkcatalyst) with respect to at least one of the foregoing performanceparameters.

The reaction inlet gas temperature in an OCM reaction catalyzed by thedisclosed nanowires can generally be maintained at a lower temperature,while maintaining better performance characteristics (e.g., conversion,C2 yield, C2 selctivity and the like) compared to the same reactioncatalyzed by a corresponding bulk catalyst under the same reactionconditions. In certain embodiments, the inlet gas temperature in an OCMreaction catalyzed by the disclosed nanowires is <700° C., <675° C.,<650° C., <625° C., <600° C., <593° C., <580° C., <570° C., <560° C.,<550° C., <540° C., <530° C., <520° C., <510° C., <500° C., <490° C.,<480° C. or even <470° C.

The reaction operating temperature in an OCM reaction catalyzed by thedisclosed nanowires can generally be maintained at a lower temperature,while maintaining better performance characteristics compared to thesame reaction catalyzed by a corresponding bulk catalyst under the samereaction conditions. In certain embodiments, the reaction operatingtemperature in an OCM reaction catalyzed by the disclosed nanowires is<700° C., <675° C., <650° C., <625° C., <600° C., <593° C., <580° C.,<570° C., <560° C., <550° C., <540° C., <530° C., <520° C., <510° C.,<500° C., <490° C., <480° C., <470° C.

The single pass methane conversion in an OCM reaction catalyzed by thenanowires is also generally better compared to the single pass methaneconversion in the same reaction catalyzed by a corresponding bulkcatalyst under the same reaction conditions. For single pass methaneconversion it ispreferably >5%, >10%, >15%, >20%, >25%, >30%, >35%, >40%, >45%, >50%, >55%, >60%, >65%, >70%, >75%,>80%.

In certain embodiments, the total reaction pressure in an OCM reactioncatalyzed by the nanowires is >1 atm, >1.1 atm, >1.2 atm, >1.3 atm, >1.4atm, >1.5 atm, >1.6 atm, >1.7 atm, >1.8 atm, >1.9 atm, >2 atm, >2.1atm, >2.1 atm, >2.2 atm, >2.3 atm, >2.4 atm, >2.5 atm, >2.6 atm, >2.7atm, >2.8 atm, >2.9 atm, >3.0 atm, >3.5 atm, >4.0 atm, >4.5 atm, >5.0atm, >5.5 atm, >6.0 atm, >6.5 atm, >7.0 atm, >7.5 atm, >8.0 atm, >8.5atm, >9.0 atm, >10.0 atm, >11.0 atm, >12.0 atm, >13.0 atm, >14.0atm, >15.0 atm, >16.0 atm, >17.0 atm, >18.0 atm, >19.0 atm or >20.0 atm.

In some embodiments, the methane partial pressure in an OCM reactioncatalyzed by the nanowires is >0.3 atm, >0.4 atm, >0.5 atm, >0.6atm, >0.7 atm, >0.8 atm, >0.9 atm, >1 atm, >1.1 atm, >1.2 atm, >1.3atm, >1.4 atm, >1.5 atm, >1.6 atm, >1.7 atm, >1.8 atm, >1.9 atm, >2.0atm, >2.1 atm, >2.2 atm, >2.3 atm, >2.4 atm, >2.5 atm, >2.6 atm, >2.7atm, >2.8 atm, >2.9 atm, >3.0 atm, >3.5 atm, >4.0 atm, >4.5 atm, >5.0atm, >5.5 atm, >6.0 atm, >6.5 atm, >7.0 atm, >7.5 atm, >8.0 atm, >8.5atm, >9.0 atm, >10.0 atm, >11.0 atm, >12.0 atm, >13.0 atm, >14.0atm, >15.0 atm, >16.0 atm, >17.0 atm, >18.0 atm, >19.0 atm or >20.0 atm.

In some embodiments, the GSHV in an OCM reaction catalyzed by thenanowiresis >20,000/hr, >50,000/hr, >75,000/hr, >100,000/hr, >120,000/hr, >130,000/hr, >150,000/hr, >200,000/hr, >250,000/hr, >300,000/hr, >350,000/hr, >400,000/hr, >450,000/hr, >500,000/hr, >750,000/hr, >1,000,000/hr, >2,000,000/hr, >3,000,000/hr,>4,000,000/hr.

In contrast to other OCM reactions, the present inventors havediscovered that OCM reactions catalyzed by the disclosed nanowires canbe performed (and still maintain high C2 yield, C2 selectivity,conversion, etc.) using O₂ sources other than pure O₂. For example, insome embodiments the O₂ source in an OCM reaction catalyzed by thedisclosed nanowires is air, oxygen enriched air, pure oxygen, oxygendiluted with nitrogen (or another inert gas) or oxygen diluted with CO₂.In certain embodiments, the O₂ source is O₂ dilutedby >99%, >98%, >97%, >96%, >95%, >94%, >93%, >92%, >91%, >90%, >85%, >80%, >75%, >70%, >65%, >60%, >55%, >50%, >45%, >40%, >35%, >30%, >25%, >20%, >15%, >10%, >9%, >8%, >7%, >6%, >5%, >4%, >3%, >2%or >1% with CO₂ or an inert gas, for example nitrogen.

The disclosed nanowires are also very stable under conditions requiredto perform any number of catalytic reactions, for example the OCMreaction. The stability of the nanowires is defined as the length oftime a catalyst will maintain its catalytic performance without asignificant decrease in performance (e.g., adecrease >20%, >15%, >10%, >5%, or greater than 1% in C2 yield, C2selectivity or conversion, etc.). In some embodiments, the nanowireshave stability under conditions required for the OCM reaction of >1hr, >5 hrs, >10 hrs, >20 hrs, >50 hrs, >80 hrs, >90 hrs, >100 hrs, >150hrs, >200 hrs, >250 hrs, >300 hrs, >350 hrs, >400 hrs, >450 hrs, >500hrs, >550 hrs, >600 hrs, >650 hrs, >700 hrs, >750 hrs, >800 hrs, >850hrs, >900 hrs, >950 hrs, >1,000 hrs, >2,000 hrs, >3,000 hrs, >4,000hrs, >5,000 hrs, >6,000 hrs, >7,000 hrs, >8,000 hrs, >9,000 hrs, >10,000hrs, >11,000 hrs, >12,000 hrs, >13,000 hrs, >14,000 hrs, >15,000hrs, >16,000 hrs, >17,000 hrs, >18,000 hrs, >19,000 hrs, >20,000 hrs, >1yrs, >2 yrs, >3 yrs, >4 yrs or >5 yrs.

In some embodiments, the ratio of ethylene to ethane in an OCM reactioncatalyzed by the nanowires is better than the ratio of ethylene toethane in an OCM reaction catalyzed by a corresponding bulk catalystunder the same conditions. In some embodiments, the ratio of ethylene toethane in an OCM reaction catalyzed by the nanowiresis >0.3, >0.4, >0.5, >0.6, >0.7, >0.8, >0.9, >1, >1.1, >1.2, >1.3, >1.4, >1.5, >1.6, >1.7, >1.8, >1.9, >2.0, >2.1, >2.2, >2.3, >2.4, >2.5, >2.6, >2.7, >2.8, >2.9, >3.0, >3.5, >4.0, >4.5, >5.0, >5.5, >6.0, >6.5, >7.0, >7.5, >8.0, >8.5, >9.0, >9.5,>10.0.

As noted above, the OCM reaction employing known bulk catalysts suffersfrom poor yield, selectivity, or conversion. In contrast to acorresponding bulk catalyst, Applicants have found that certainnanowires, for example the exemplary nanowires disclosed herein, possesa catalytic activity in the OCM reaction such that the yield,selectivity, and/or conversion is better than when the OCM reaction iscatalyzed by a corresponding bulk catalyst. In one embodiment, thedisclosure provides a nanowire having a catalytic activity such that theconversion of methane to ethylene in the oxidative coupling of methanereaction is greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0times, 3.0 times, or 4.0 times the conversion of methane to ethylenecompared to the same reaction under the same conditions but performedwith a catalyst prepared from bulk material having the same chemicalcomposition as the nanowire. In other embodiments, the conversion ofmethane to ethylene in an OCM reaction catalyzed by the nanowire isgreater than 10%, greater than 20%, greater than 30%, greater than 50%,greater than 75%, or greater than 90%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the yield of ethylene in the oxidativecoupling of methane reaction is greater than at least 1.1 times, 1.25times, 1.50 times, 2.0 times, 3.0 times, or 4.0 times the yield ofethylene compared to the same reaction under the same conditions butperformed with a catalyst prepared from bulk material having the samechemical composition as the nanowire. In some embodiments the yield ofethylene in an OCM reaction catalyzed by the nanowire is greater than10%, greater than 20%, greater than 30%, greater than 50%, greater than75%, or greater than 90%.

As noted above, the OCM reaction employing known bulk catalysts suffersfrom poor yield, selectivity, or conversion. In contrast to acorresponding bulk catalyst, Applicants have found that certainnanowires, for example the exemplary nanowires disclosed herein, possesa catalytic activity in the OCM reaction such that the yield,selectivity, and/or conversion is better than when the OCM reaction iscatalyzed by a corresponding bulk catalyst. In one embodiment, thedisclosure provides a nanowire having a catalytic activity such that theconversion of methane in the oxidative coupling of methane reaction isgreater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0times, or 4.0 times the conversion of methane compared to the samereaction under the same conditions but performed with a catalystprepared from bulk material having the same chemical composition as thenanowire. In other embodiments, the conversion of methane in an OCMreaction catalyzed by the nanowire is greater than 10%, greater than20%, greater than 30%, greater than 50%, greater than 75%, or greaterthan 90%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the C2 yield in the oxidative coupling ofmethane reaction is greater than at least 1.1 times, 1.25 times, 1.50times, 2.0 times, 3.0 times, or 4.0 times the C2 yield compared to thesame reaction under the same conditions but performed with a catalystprepared from bulk material having the same chemical composition as thenanowire. In some embodiments the C2 yield in an OCM reaction catalyzedby the nanowire is greater than 10%, greater than 20%, greater than 30%,greater than 50%, greater than 75%, or greater than 90%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity in the OCM reaction such that the nanowire has thesame catalytic activity (i.e., same selectivity, conversion or yield),but at a lower temperature, compared a catalyst prepared from bulkmaterial having the same chemical composition as the nanowire. In someembodiments the catalytic activity of the nanowires in the OCM reactionis the same as the catalytic activity of a catalyst prepared from bulkmaterial having the same chemical composition as the nanowire, but at atemperature of at least 20° C. less. In some embodiments the catalyticactivity of the nanowires in the OCM reaction is the same as thecatalytic activity of a catalyst prepared from bulk material having thesame chemical composition as the nanowire, but at a temperature of atleast 50° C. less. In some embodiments the catalytic activity of thenanowires in the OCM reaction is the same as the catalytic activity of acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire, but at a temperature of at least 100° C.less. In some embodiments the catalytic activity of the nanowires in theOCM reaction is the same as the catalytic activity of a catalystprepared from bulk material having the same chemical composition as thenanowire, but at a temperature of at least 200° C. less.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the selectivity for CO or CO₂ in theoxidative coupling of methane reaction is less than at least 0.9 times,0.8 times, 0.5 times, 0.2 times, or 0.1 times the selectivity for CO orCO₂ compared to the same reaction under the same conditions butperformed with a catalyst prepared from bulk material having the samechemical composition as the nanowire.

In some other embodiments, a method for converting methane into ethylenecomprising use of catalyst mixture comprising two or more catalysts isprovided. For example, the catalyst mixture may be a mixture of acatalyst having good OCM activity and a catalyst having good ODHactivity. Such catalyst mixture are described in more detail above.

Typically, the OCM reaction is run in a mixture of oxygen and nitrogenor other inert gas. Such gasses are expensive and increase the overallproduction costs associated with preparation of ethylene or ethane frommethane. However, the present inventors have now discovered that suchexpensive gases are not required and high yield, conversion,selectivity, etc. can be obtained when air is used as the gas mixtureinstead of pre-packaged and purified sources of oxygen and other gases.Accordingly, in one embodiment the disclosure provides a method forperforming the OCM reaction in air.

In addition to air or O₂ gas, the presently disclosed nanowires andassociated methods provide for use of other sources of oxygen in the OCMreaction. In this respect, an alternate source of oxygen such a CO₂,H₂O, SO₂ or SO₃ may be used either in place of, or in addition to, airor oxygen as the oxygen source. Such methods have the potential toincrease the efficiency of the OCM reaction, for example by consuming areaction byproduct (e.g., CO₂ or H₂O) and controlling the OCM exothermas described below.

As noted above, in the OCM reaction, methane is oxidatively converted tomethyl radicals, which are then coupled to form ethane, which issubsequently oxidized to ethylene. In traditional OCM reactions, theoxidation agent for both the methyl radical formation and the ethaneoxidation to ethylene is oxygen. In order to minimize full oxidation ofmethane or ethane to carbon dioxide, i.e. maximize C2 selectivity, themethane to oxygen ratio is generally kept at 4 (i.e. full conversion ofmethane into methyl radicals) or above. As a result, the OCM reaction istypically oxygen limited and thus the oxygen concentration in theeffluent is zero.

Accordingly, in one embodiment the present disclosure provides a methodfor increasing the methane conversion and increasing, or in someembodiments, not reducing, the C2 selectivity in an OCM reaction. Thedisclosed methods include adding to a traditional OCM catalyst anotherOCM catalyst that uses an oxygen source other than molecular oxygen. Insome embodiments, the alternate oxygen source is CO₂, H₂O, SO₂, SO₃ orcombinations thereof. For example in some embodiments, the alternateoxygen source is CO₂. In other embodiments the alternate oxygen sourceis H₂O.

Because C2 selectivity is typically between 50% and 80% in the OCMreaction, OCM typically produces significant amounts of CO₂ as abyproduct (CO₂ selectivity can typically range from 20-50%).Additionally, H₂O is produced in copious amounts, regardless of the C2selectivity. Therefore both CO₂ and H₂O would are attractive oxygensources for OCM in an O₂ depleted environment.

Accordingly, one embodiment of the present disclosure provides acatalyst (and related methods for use thereof) which is catalytic in theOCM reaction and which uses CO₂, H₂O, SO₂, SO₃ or another alternativeoxygen source or combinations thereof as a source of oxygen. Otherembodiments, provide a catalytic material comprising two or morecatalysts, wherein the catalytic material comprises at least onecatalyst which is catalytic in the OCM reaction and uses O₂ for at leastone oxygen source and at least one catalysts which is catalytic in theOCM reaction and uses at least of CO₂, H₂O, SO₂, SO₃, NO, NO₂, NO₃ oranother alternative oxygen source. Methods for performing the OCMreaction with such catalytic materials are also provided. Such catalystscomprise any of the compositions disclosed herein and are effective ascatalysts in an OCM reaction using an alternative oxygen source attemperatures of 900° C. or lower, 850° C. or lower, 800° C. or lower,750° C. or lower, 700° C. or lower or even 650° C. or lower. In someembodiments of the above, the catalyst is a nanowire catalyst.

Examples of OCM catalysts that use CO₂ or other oxygen sources ratherthan O₂ include, but are not limited to, catalysts comprising La₂O₃/ZnO,CeO₂/ZnO, CaO/ZnO, CaO/CeO₂, CaO/Cr₂O₃, CaO/MnO₂, SrO/ZnO, SrO/CeO₂,SrO/Cr₂O₃, SrO/MnO₂, SrCO₃/MnO₂, BaO/ZnO, BaO/CeO₂, BaO/Cr₂O₃, BaO/MnO₂,CaO/MnO/CeO₂, Na₂WO₄/Mn/SiO₂, Pr₂O₃, Tb₂O₃.

Some embodiments provide a method for performing OCM, wherein a mixtureof an OCM catalyst which use O₂ as an oxygen source (referred to hereinas an O₂-OCM catalyst) and an OCM catalyst which use CO₂ as an oxygensource (referred to herein as a CO₂-OCM catalyst) is employed as thecatalytic material, for example in a catalyst bed. Such methods havecertain advantages. For example, the CO₂-OCM reaction is endothermic andthe O₂-OCM reaction is exothermic, and thus if the right mixture and/orarrangement of CO₂-OCM and O₂-OCM catalysts is used, the methods areparticularly useful for controlling the exotherm of the OCM reaction. Insome embodiments, the catalyst bed comprises a mixture of O₂-OCMcatalyst and CO₂-OCM catalysts. The mixture may be in a ratio of 1:99 to99:1. The two catalysts work synergistically as the O₂-OCM catalystsupplies the CO₂-OCM catalyst with the necessary carbon dioxide and theendothermic nature of the C₂-OCM reaction serves to control the exothermof the overall reaction. Alternatively, the CO₂ source may be externalto the reaction (e.g., fed in from a CO₂ tank, or other source) and/orthe heat required for the CO₂-OCM reaction is supplied from an externalsource (e.g., heating the reactor).

Since the gas composition will tend to become enriched in CO₂ as itflows through the catalyst bed (i.e., as the OCM reaction proceeds, moreCO₂ is produced), some embodiments of the present invention provide anOCM method wherein the catalyst bed comprises a gradient of catalystswhich changes from a high concentration of O₂-OCM catalysts at the frontof the bed to a high concentration of CO₂-OCM catalysts at the end ofthe catalyst bed.

The O₂-OCM catalyst and CO₂ OCM catalyst may have the same or differentcompositions. For example, in some embodiments the O₂-OCM catalyst andCO₂-OCM catalyst have the same composition but different morphologies(e.g., nanowire, bent nanowire, bulk, etc.). In other embodiments theO₂-OCM and the CO₂-OCM catalyst have different compositions.

Furthermore, CO₂-OCM catalysts will typically have higher selectivity,but lower yields than an O₂-OCM catalyst. Accordingly, in one embodimentthe methods comprise use of a mixture of an O₂-OCM catalyst and aCO₂-OCM catalyst and performing the reaction in O₂ deprived environmentso that the CO₂-OCM reaction is favored and the selectivity isincreased. Under appropriate conditions the yield and selectivity of theOCM reaction can thus be optimized.

In some other embodiments, the catalyst bed comprises a mixture of oneor more low temperature O₂-OCM catalyst (i.e., a catalyst active at lowtemperatures, for example less than 700° C.) and one or more hightemperature CO₂-OCM catalyst (i.e., a catalyst active at hightemperatures, for example 800° C. or higher). Here, the required hightemperature for the CO₂-OCM may be provided by the hotspots produced bythe O₂-OCM catalyst. In such a scenario, the mixture may be sufficientlycoarse such that the hotspots are not being excessively cooled down byexcessive dilution effect.

In other embodiments, the catalyst bed comprises alternating layers ofO₂-OCM and CO₂-OCM catalysts. The catalyst layer stack may begin with alayer of O₂-OCM catalyst, so that it can supply the next layer (e.g., aCO₂-OCM layer) with the necessary CO₂. The O₂-OCM layer thickness may beoptimized to be the smallest at which O₂ conversion is 100% and thus theCH₄ conversion of the layer is maximized. The catalyst bed may compriseany number of catalyst layers, for example the overall number of layersmay be optimized to maximize the overall CH₄ conversion and C2selectivity.

In some embodiments, the catalyst bed comprises alternating layers oflow temperature O₂-OCM catalysts and high temperature CO₂-OCM catalysts.Since the CO₂-OCM reaction is endothermic, the layers of CO₂-OCMcatalyst may be sufficiently thin such that in can be “warmed up” by thehotspots of the O₂-OCM layers. The endothermic nature of the CO₂-OCMreaction can be advantageous for the overall thermal management of anOCM reactor. In some embodiments, the CO₂-OCM catalyst layers act as“internal” cooling for the O₂-OCM layers, thus simplifying therequirements for the cooling, for example in a tubular reactor.Therefore, an interesting cycle takes place with the endothermicreaction providing the necessary heat for the endothermic reaction andthe endothermic reaction providing the necessary cooling for theexothermic reaction.

Accordingly, one embodiment of the present invention is a method for theoxidative coupling of methane, wherein the method comprises conversionof methane to ethane and/or ethylene in the presence of a catalyticmaterial, and wherein the catalytic material comprises a bed ofalternating layers of O₂-OCM catalysts and CO₂-OCM catalysts. In otherembodiments the bed comprises a mixture (i.e., not alternating layers)of O₂-OCM catalysts and CO₂-OCM catalysts.

In other embodiments, the OCM methods include use of a jacketed reactorwith the exothermic O₂-OCM reaction in the core and the endothermicCO₂-OCM reaction in the mantel. In other embodiments, the unused CO₂ canbe recycled and reinjected into the reactor, optionally with therecycled CH₄. Additional CO₂ can also be injected to increase theoverall methane conversion and help reduce greenhouse gases.

In other embodiments, the reactor comprises alternating stages of O₂-OCMcatalyst beds and CO₂-OCM catalyst beds. The CO₂ necessary for theCO₂-OCM stages is provided by the O₂-OCM stage upstream. Additional CO₂may also be injected. The O₂ necessary for the subsequent O₂-OCM stagesis injected downstream from the CO₂-OCM stages. The CO₂-OCM stages mayprovide the necessary cooling for the O₂-OCM stages. Alternatively,separate cooling may be provided. Likewise, if necessary the inlet gasof the CO₂-OCM stages can be additionally heated, the CO₂-OCM bed can beheated or both.

In related embodiments, the CO₂ naturally occurring in natural gas isnot removed prior to performing the OCM, alternatively CO2 is added tothe feed with the recycled methane. Instead the CO₂ containing naturalgas is used as a feedstock for CO₂-OCM, thus potentially saving aseparation step. The amount of naturally occurring CO₂ in natural gasdepends on the well and the methods can be adjusted accordinglydepending on the source of the natural gas.

The foregoing methods can be generalized as a method to control thetemperature of very exothermic reactions by coupling them with anendothermic reaction that uses the same feedstock (or byproducts of theexothermic reaction) to make the same product (or a related product).This concept can be reversed, i.e. providing heat to an endothermicreaction by coupling it with an exothermic reaction. This will alsoallow a higher per pass yield in the OCM reactor.

For purpose of simplicity, the above description relating to the use ofO₂-OCM and CO₂-OCM catalysts was described in reference to the oxidativecoupling of methane (OCM); however, the same concept is applicable toother catalytic reactions including but not limited to: oxidativedehydrogenation (ODH) of alkanes to their corresponding alkenes,selective oxidation of alkanes and alkenes and alkynes, etc. Forexample, in a related embodiment, a catalyst capable of using analternative oxygen source (e.g., CO₂, H₂O, SO₂, SO₃ or combinationsthereof) to catalyze the oxidative dehydrogenation of ethane isprovided. Such catalysts, and uses thereof are described in more detailbelow.

Furthermore, the above methods are applicable for creating novelcatalysts by blending catalysts that use different reactants for thesame catalytic reactions, for example different oxidants for anoxidation reaction and at least one oxidant is a byproduct of one of thecatalytic reactions. In addition, the methods can also be generalizedfor internal temperature control of reactors by blending catalysts thatcatalyze reactions that share the same or similar products but areexothermic and endothermic, respectively. These two concepts can also becoupled together.

2. Oxidative Dehydrogenation

Worldwide demand for alkenes, especially ethylene and propylene, ishigh. The main sources for alkenes include steam cracking,fluid-catalytic-cracking and catalytic dehydrogenation. The currentindustrial processes for producing alkenes, including ethylene andpropylene, suffer from some of the same disadvantages described abovefor the OCM reaction. Accordingly, a process for the preparation ofalkenes, which is more energy efficient and has higher yield,selectivity, and conversion than current processes is needed. Applicantshave now found that nanowires, for example the exemplary nanowiresdisclosed herein, fulfill this need and provide related advantages.

In one embodiment, the disclosed nanowires are useful as catalysts forthe oxidative dehydrogenation (ODH) of hydrocarbons (e.g. alkanes,alkenes, and alkynes). For example, in one embodiment the nanowires areuseful as catalysts in an ODH reaction for the conversion of ethane orpropane to ethylene or propylene, respectively. Reaction scheme (9)depicts the oxidative dehydrogenation of hydrocarbons:

C_(x)H_(y)+½O₂→C_(x)H_(y-2)+H₂O  (9)

Representative catalysts useful for the ODH reaction include, but arenot limited to nanowires comprising Zr, V, Mo, Ba, Nd, Ce, Ti, Mg, Nb,La, Sr, Sm, Cr, W, Y or Ca or oxides or combinations thereof. Activatingpromoters (i.e. dopants) comprising P, K, Ca, Ni, Cr, Nb, Mg, Au, Zn, orMo, or combinations thereof, may also be employed.

As noted above, improvements to the yield, selectivity, and/orconversion in the ODH reaction employing bulk catalysts are needed.Accordingly, in one embodiment, the present disclosure provides ananowire which posses a catalytic activity in the ODH reaction such thatthe yield, selectivity, and/or conversion is better than when the ODHreaction is catalyzed by a corresponding bulk catalyst. In oneembodiment, the disclosure provides a nanowire having a catalyticactivity such that the conversion of hydrocarbon to alkene in the ODHreaction is greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0times, 3.0 times, or 4.0 times the conversion of alkane to alkenecompared to the same reaction under the same conditions but performedwith a catalyst prepared from bulk material having the same chemicalcomposition as the nanowire. In other embodiments, the conversion ofhydrocarbon to alkene in an ODH reaction catalyzed by the nanowire isgreater than 10%, greater than 20%, greater than 30%, greater than 50%,greater than 75%, or greater than 90%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the yield of alkene in an ODH reaction isgreater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0times, or 4.0 times the yield of alkenes compared to the same reactionunder the same conditions but performed with a catalyst prepared frombulk material having the same chemical composition as the nanowire. Insome embodiments the yield of alkene in an ODH reaction catalyzed by thenanowire is greater than 10%, greater than 20%, greater than 30%,greater than 50%, greater than 75%, or greater than 90%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity in the ODH reaction such that the nanowire has thesame catalytic activity, but at a lower temperature, compared a catalystprepared from bulk material having the same chemical composition as thenanowire. In some embodiments the catalytic activity of the nanowires inthe ODH reaction is the same or better than the catalytic activity of acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire, but at a temperature of at least 20° C.less. In some embodiments the catalytic activity of the nanowires in theODH reaction is the same or better than the catalytic activity of acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire, but at a temperature of at least 50° C.less. In some embodiments the catalytic activity of the nanowires in theODH reaction is the same or better than the catalytic activity of acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire, but at a temperature of at least 100° C.less. In some embodiments the catalytic activity of the nanowires in theODH reaction is the same or better than the catalytic activity of acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire, but at a temperature of at least 200° C.less.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the selectivity for alkenes in an ODHreaction is greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0times, 3.0 times, or 4.0 times the selectivity for alkenes compared tothe same reaction under the same conditions but performed with acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire. In other embodiments, the selectivity foralkenes in an ODH reaction catalyzed by the nanowire is greater than50%, greater than 60%, greater than 70%, greater than 80%, greater than90%, or greater than 95%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the selectivity for CO or CO₂ in an ODHreaction is less than at least 0.9 times, 0.8 times, 0.5 times, 0.2times, or 0.1 times the selectivity for CO or CO₂ compared to the samereaction under the same conditions but performed with a catalystprepared from bulk material having the same chemical composition as thenanowire.

In one embodiment, the nanowires disclosed herein enable efficientconversion of hydrocarbon to alkene in the ODH reaction at temperaturesless than when the corresponding bulk material is used as a catalyst.For example, in one embodiment, the nanowires disclosed herein enableefficient conversion (i.e. high yield, conversion, and/or selectivity)of hydrocarbon to alkene at temperatures of less than 800° C., less than700° C., less than 600° C., less than 500° C., less than 400° C., orless than 300° C.

The stability of the nanowires is defined as the length of time acatalyst will maintain its catalytic performance without a significantdecrease in performance (e.g., a decrease >20%, >15%, >10%, >5%, orgreater than 1% in ODH activity or alkene selectivity, etc.). In someembodiments, the nanowires have stability under conditions required forthe ODH reaction of >1 hr, >5 hrs, >10 hrs, >20 hrs, >50 hrs, >80hrs, >90 hrs, >100 hrs, >150 hrs, >200 hrs, >250 hrs, >300 hrs, >350hrs, >400 hrs, >450 hrs, >500 hrs, >550 hrs, >600 hrs, >650 hrs, >700hrs, >750 hrs, >800 hrs, >850 hrs, >900 hrs, >950 hrs, >1,000hrs, >2,000 hrs, >3,000 hrs, >4,000 hrs, >5,000 hrs, >6,000 hrs, >7,000hrs, >8,000 hrs, >9,000 hrs, >10,000 hrs, >11,000 hrs, >12,000hrs, >13,000 hrs, >14,000 hrs, >15,000 hrs, >16,000 hrs, >17,000hrs, >18,000 hrs, >19,000 hrs, >20,000 hrs, >1 yrs, >2 yrs, >3 yrs, >4yrs or >5 yrs.

As noted above, one embodiment of the present disclosure is directed toa catalyst capable of using an alternative oxygen source (e.g., CO₂,H₂O, SO₂, SO₃ or combinations thereof) to catalyze the oxidativedehydrogenation of ethane is provided. For example, the ODH reaction mayproceed according to the following reaction (10):

CO₂+C_(x)H_(y)→C_(x)H_(y-2)+CO+H₂O  (10)

wherein x is an interger and Y is 2x+2. Compositions useful in thisregard include Fe₂O₃, Cr₂O₃, MnO₂, Ga₂O₃, Cr/SiO₂, Cr/SO₄—SiO₂,Cr—K/SO₄—SiO₂, Na₂WO₄—Mn/SiO₂, Cr-HZSM-5, Cr/Si-MCM-41 (Cr-HZSM-5 andCr/Si-MCM-41 refer to known zeolites) and MoC/SiO₂. In some embodiments,any of the foregoing catalyst compositions may be supported on SiO₂,ZrO₂, Al₂O₃, TiO₂ or combinations thereof. In certain embodiments, thecatalyst may be a nanowire catalyst and in other embodiments thecatalyst is a bulk catalyst.

The catalysts having ODH activity with alternative oxygen sources (e.g.,CO₂, referred to herein as a CO₂-ODH catalyst) have a number ofadvantages. For example, in some embodiments a method for convertingmethane to ethylene comprises use of an O₂-OCM catalyst in the presenceof a CO₂-ODH catalyst is provided. Catalytic materials comprising atleast one O₂-OCM catalyst and at least one CO₂-ODH catalyst are alsoprovided in some embodiments. This combination of catalysts results in ahigher yield of ethylene (and/or ratio of ethylene to ethane) since theCO₂ produced by the OCM reaction is consumed and used to convert ethaneto ethylene.

In one embodiment, a method for preparation of ethylene comprisesconverting methane to ethylene in the presence of two or more catalysts,wherein at least one catalyst is an O₂-OCM catalyst and at least onecatalyst is a CO₂-ODH catalyst. Such methods have certain advantages.For example, the CO2-ODH reaction is endothermic and the O₂-OCM reactionis exothermic, and thus if the right mixture and/or arrangement ofCO₂-ODH and O₂-OCM catalysts is used, the methods are particularlyuseful for controlling the exotherm of the OCM reaction. In someembodiments, the catalyst bed comprises a mixture of O₂-OCM catalyst andCO2-ODH catalysts. The mixture may be in a ratio of 1:99 to 99:1. Thetwo catalysts work synergistically as the O₂-OCM catalyst supplies theCO₂-ODH catalyst with the necessary carbon dioxide and the endothermicnature of the C₂-OCM reaction serves to control the exotherm of theoverall reaction.

Since the gas composition will tend to become enriched in CO₂ as itflows through the catalyst bed (i.e., as the OCM reaction proceeds, moreCO₂ is produced), some embodiments of the present invention provide anOCM method wherien the catalyst bed comprises a gradient of catalystswhich changes from a high concentration of O₂-OCM catalysts at the frontof the bed to a high concentration of CO₂-ODH catalysts at the end ofthe catalyst bed.

The O₂-ODH catalyst and CO₂-ODH catalyst may have the same or differentcompositions. For example, in some embodiments the O₂-ODH catalyst andCO₂-ODH catalyst have the same composition but different morphologies(e.g., nanowire, bent nanowire, bulk, etc.). In other embodiments theO₂-ODH and the CO₂-ODH catalyst have different compositions.

In other embodiments, the catalyst bed comprises alternating layers ofO₂-OCM and CO₂-ODH catalysts. The catalyst layer stack may begin with alayer of O₂-OCM catalyst, so that it can supply the next layer (e.g., aCO2-ODH layer) with the necessary CO₂. The O₂-OCM layer thickness may beoptimized to be the smallest at which O2 conversion is 100% and thus theCH₄ conversion of the layer is maximized. The catalyst bed may compriseany number of catalyst layers, for example the overall number of layersmay be optimized to maximize the overall CH₄ conversion and C2selectivity.

In some embodiments, the catalyst bed comprises alternating layers oflow temperature O₂-OCM catalysts and high temperature CO₂-ODH catalysts.Since the CO₂-ODH reaction is endothermic, the layers of CO₂-ODHcatalyst may be sufficiently thin such that in can be “warmed up” by thehotspots of the O₂-OCM layers. The endothermic nature of the CO₂-ODHreaction can be advantageous for the overall thermal management of anOCM reactor. In some embodiments, the CO₂-ODH catalyst layers act as“internal” cooling for the O₂-OCM layers, thus simplifying therequirements for the cooling, for example in a tubular reactor.Therefore, an interesting cycle takes place with the endothermicreaction providing the necessary heat for the endothermic reaction andthe endothermic reaction providing the necessary cooling for theexothermic reaction.

Accordingly, one embodiment of the present invention is a method for theoxidative coupling of methane, wherein the method comprises conversionof methane to ethane and/or ethylene in the presence of a catalyticmaterial, and wherein the catalytic material comprises a bed ofalternating layers of O₂-OCM catalysts and CO₂-ODH catalysts. In otherembodiments the bed comprises a mixture (i.e., not alternating layers)of O₂-OCM catalysts and CO₂-ODH catalysts. Such methods increase theethylene yield and/or ratio of ethylene to ethane compared to otherknown methods.

In other embodiments, the OCM methods include use of a jacketed reactorwith the exothermic O₂-OCM reaction in the core and the endothermicCO₂-ODH reaction in the mantel. In other embodiments, the unused CO₂ canbe recycled and reinjected into the reactor, optionally with therecycled CH₄. Additional CO₂ can also be injected to increase theoverall methane conversion and help reduce greenhouse gases.

In other embodiments, the reactor comprises alternating stages of O₂-OCMcatalyst beds and CO₂-ODH catalyst beds. The CO₂ necessary for theCO₂-ODH stages is provided by the O₂-OCM stage upstream. Additional CO₂may also be injected. The O₂ necessary for the subsequent O2-OCM stagesis injected downstream from the CO₂-ODH stages. The CO₂-ODH stages mayprovide the necessary cooling for the O₂-OCM stages. Alternatively,separate cooling may be provided. Likewise, if necessary the inlet gasof the CO₂-ODH stages can be additionally heated, the CO₂-ODH bed can beheated or both.

In related embodiments, the CO₂ naturally occurring in natural gas isnot removed prior to performing the OCM, alternatively CO₂ is added tothe feed with the recycled methane. Instead the CO₂ containing naturalgas is used as a feedstock for CO₂-ODH, thus potentially saving aseparation step. The amount of naturally occurring CO₂ in natural gasdepends on the well and the methods can be adjusted accordinglydepending on the source of the natural gas.

3. Carbon dioxide reforming of methane

Carbon dioxide reforming (CDR) of methane is an attractive process forconverting CO₂ in process streams or naturally occurring sources intothe valuable chemical product, syngas (a mixture of hydrogen and carbonmonoxide). Syngas can then be manufactured into a wide range ofhydrocarbon products through processes such as the Fischer-Tropschsynthesis (discussed below) to form liquid fuels including methanol,ethanol, diesel, and gasoline. The result is a powerful technique to notonly remove CO₂ emissions but also create a new alternative source forfuels that are not derived from petroleum crude oil. The CDR reactionwith methane is exemplified in reaction scheme (11).

CO₂+CH₄→2CO+2H₂  (11)

Unfortunately, no established industrial technology for CDR exists todayin spite of its tremendous potential value. While not wishing to bebound by theory, it is thought that the primary problem with CDR is dueto side-reactions from catalyst deactiviation induced by carbondeposition via the Boudouard reaction (reaction scheme (12)) and/ormethane cracking (reaction scheme (13)) resulting from the hightemperature reaction conditions. The occurrence of the coking effect isintimately related to the complex reaction mechanism, and the associatedreaction kinetics of the catalysts employed in the reaction.

2CO→C+CO₂  (12)

CH₄→C+2H₂  (13)

While not wishing to be bound by theory, the CDR reaction is thought toproceed through a multistep surface reaction mechanism. FIG. 9schematically depicts a CDR reaction 700, in which activation anddissociation of CH₄ occurs on the metal catalyst surface 710 to formintermediate “M-C”. At the same time, absorption and activation of CO₂takes place at the oxide support surface 720 to provide intermediate“S—CO₂”, since the carbon in a CO₂ molecule as a Lewis acid tends toreact with the Lewis base center of an oxide. The final step is thereaction between the M-C species and the activated S—CO₂ to form CO.

In one embodiment, the present disclosure provides nanowires, forexample the exemplary nanowires disclosed herein, which are useful ascatalysts for the carbon dioxide reforming of methane. For example, inone embodiment the nanowires are useful as catalysts in a CDR reactionfor the production of syn gas.

Improvements to the yield, selectivity, and/or conversion in the CDRreaction employing bulk catalysts are needed. Accordingly, in oneembodiment, the nanowires posses a catalytic activity in the CDRreaction such that the yield, selectivity, and/or conversion is betterthan when the CDR reaction is catalyzed by a corresponding bulkcatalyst. In one embodiment, the disclosure provides a nanowire having acatalytic activity such that the conversion of CO₂ to CO in the CDRreaction is greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0times, 3.0 times, or 4.0 times the conversion of CO₂ to CO compared tothe same reaction under the same conditions but performed with acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire. In other embodiments, the conversion of CO₂to CO in a CDR reaction catalyzed by the nanowire is greater than 10%,greater than 20%, greater than 30%, greater than 50%, greater than 75%,or greater than 90%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the yield of CO in a CDR reaction isgreater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0times, or 4.0 times the yield of CO compared to the same reaction underthe same conditions but performed with a catalyst prepared from bulkmaterial having the same chemical composition as the nanowire. In someembodiments the yield of CO in a CDR reaction catalyzed by the nanowireis greater than 10%, greater than 20%, greater than 30%, greater than50%, greater than 75%, or greater than 90%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity in a CDR reaction such that the nanowire has the sameor better catalytic activity, but at a lower temperature, compared acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire. In some embodiments the catalytic activityof the nanowires in a CDR reaction is the same or better than thecatalytic activity of a catalyst prepared from bulk material having thesame chemical composition as the nanowire, but at a temperature of atleast 20° C. less. In some embodiments the catalytic activity of thenanowires in a CDR reaction is the same or better than the catalyticactivity of a catalyst prepared from bulk material having the samechemical composition as the nanowire, but at a temperature of at least50° C. less. In some embodiments the catalytic activity of the nanowiresin a CDR reaction is the same or better than the catalytic activity of acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire, but at a temperature of at least 100° C.less. In some embodiments the catalytic activity of the nanowires in aCDR reaction is the same or better than the catalytic activity of acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire, but at a temperature of at least 200° C.less.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the selectivity for CO in a CDR reaction isgreater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0times, or 4.0 times the selectivity for CO compared to the same reactionunder the same conditions but performed with a catalyst prepared frombulk material having the same chemical composition as the nanowire. Inother embodiments, the selectivity for CO in a CDR reaction catalyzed bythe nanowire is greater than 10%, greater than 20%, greater than 30%,greater than 50%, greater than 75%, or greater than 90%.

In one embodiment, the nanowires disclosed herein enable efficientconversion of CO₂ to CO in the CDR reaction at temperatures less thanwhen the corresponding bulk material is used as a catalyst. For example,in one embodiment, the nanowires enable efficient conversion (i.e., highyield, conversion, and/or selectivity) of CO₂ to CO at temperatures ofless than 900° C., less than 800° C., less than 700° C., less than 600°C., or less than 500° C.

4. Fischer-Tropsch Synthesis

Fischer-Tropsch synthesis (FTS) is a valuable process for convertingsynthesis gas (i.e., CO and H₂) into valuable hydrocarbon fuels, forexample, light alkenes, gasoline, diesel fuel, etc. FTS has thepotential to reduce the current reliance on the petroleum reserve andtake advantage of the abundance of coal and natural gas reserves.Current FTS processes suffer from poor yield, selectivity, conversion,catalyst deactivation, poor thermal efficiency and other relateddisadvantages. Production of alkanes via FTS is shown in reaction scheme(14), wherein n is an integer.

CO+2H₂→(1/n)(C_(n)H_(2n))+H₂O  (14)

In one embodiment, nanowires are provided which are useful as catalystsin FTS processes. For example, in one embodiment the nanowires areuseful as catalysts in a FTS process for the production of alkanes.

Improvements to the yield, selectivity, and/or conversion in FTSprocesses employing bulk catalysts are needed. Accordingly, in oneembodiment, the nanowires posses a catalytic activity in an FTS processsuch that the yield, selectivity, and/or conversion is better than whenthe FTS process is catalyzed by a corresponding bulk catalyst. In oneembodiment, the disclosure provides a nanowire having a catalyticactivity such that the conversion of CO to alkane in an FTS process isgreater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0times, or 4.0 times the conversion of CO to alkane compared to the samereaction under the same conditions but performed with a catalystprepared from bulk material having the same chemical composition as thenanowire. In other embodiments, the conversion of CO to alkane in an FTSprocess catalyzed by the nanowire is greater than 10%, greater than 20%,greater than 30%, greater than 50%, greater than 75%, or greater than90%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity in an FTS process such that the nanowire has the sameor better catalytic activity, but at a lower temperature, compared acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire. In some embodiments the catalytic activityof the nanowires in an FTS process is the same or better than thecatalytic activity of a catalyst prepared from bulk material having thesame chemical composition as the nanowire, but at a temperature of atleast 20° C. less. In some embodiments the catalytic activity of thenanowires in an FTS process is the same or better than the catalyticactivity of a catalyst prepared from bulk material having the samechemical composition as the nanowire, but at a temperature of at least50° C. less. In some embodiments the catalytic activity of the nanowiresin an FTS process is the same or better than the catalytic activity of acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire, but at a temperature of at least 100° C.less. In some embodiments the catalytic activity of the nanowires in anFTS process is the same or better than the catalytic activity of acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire, but at a temperature of at least 200° C.less.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the yield of alkane in a FTS process isgreater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0times, or 4.0 times the yield of alkane compared to the same reactionunder the same conditions but performed with a catalyst prepared frombulk material having the same chemical composition as the nanowire. Insome embodiments the yield of alkane in an FTS process catalyzed by thenanowire is greater than 10%, greater than 20%, greater than 30%,greater than 50%, greater than 75%, or greater than 90%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the selectivity for alkanes in an FTSprocess is greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0times, 3.0 times, or 4.0 times the selectivity for alkanes compared tothe same reaction under the same conditions but performed with acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire. In other embodiments, the selectivity foralkanes in an FTS process catalyzed by the nanowire is greater than 10%,greater than 20%, greater than 30%, greater than 50%, greater than 75%,or greater than 90%.

In one embodiment, the nanowires disclosed herein enable efficientconversion of CO to alkanes in a CDR process at temperatures less thanwhen the corresponding bulk material is used as a catalyst. For example,in one embodiment, the nanowires enable efficient conversion (i.e., highyield, conversion, and/or selectivity) of CO to alkanes at temperaturesof less than 400° C., less than 300° C., less than 250° C., less than200° C., less the 150° C., less than 100° C. or less than 50° C.

5. Oxidation of CO

Carbon monoxide (CO) is a toxic gas and can convert hemoglobin tocarboxyhemoglobin resulting in asphyxiation. Dangerous levels of CO canbe reduced by oxidation of CO to CO₂ as shown in reaction scheme 15:

CO+½O₂→CO₂  (15)

Catalysts for the conversion of CO into CO₂ have been developed butimprovements to the known catalysts are needed. Accordingly in oneembodiment, the present disclosure provides nanowires useful ascatalysts for the oxidation of CO to CO₂.

In one embodiment, the nanowires posses a catalytic activity in aprocess for the conversion of CO into CO₂ such that the yield,selectivity, and/or conversion is better than when the oxidation of COinto CO₂ is catalyzed by a corresponding bulk catalyst. In oneembodiment, the disclosure provides a nanowire having a catalyticactivity such that the conversion of CO to CO₂ is greater than at least1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0 times, or 4.0 timesthe conversion of CO to CO₂ compared to the same reaction under the sameconditions but performed with a catalyst prepared from bulk material andhaving the same chemical composition as the nanowire. In otherembodiments, the conversion of CO to CO₂ catalyzed by the nanowire isgreater than 10%, greater than 20%, greater than 30%, greater than 50%,greater than 75%, or greater than 90%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the yield of CO₂ from the oxidation of COis greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times,3.0 times, or 4.0 times the yield of CO₂ compared to the same reactionunder the same conditions but performed with a catalyst prepared frombulk material having the same chemical composition as the nanowire. Insome embodiments the yield of CO₂ from the oxidation of CO catalyzed bythe nanowire is greater than 10%, greater than 20%, greater than 30%,greater than 50%, greater than 75%, or greater than 90%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity in an oxidation of CO reaction such that the nanowirehas the same or better catalytic activity, but at a lower temperature,compared a catalyst prepared from bulk material having the same chemicalcomposition as the nanowire. In some embodiments the catalytic activityof the nanowires in an oxidation of CO reaction is the same or betterthan the catalytic activity of a catalyst prepared from bulk materialhaving the same chemical composition as the nanowire, but at atemperature of at least 20° C. less. In some embodiments the catalyticactivity of the nanowires in an oxidation of CO reaction is the same orbetter than the catalytic activity of a catalyst prepared from bulkmaterial having the same chemical composition as the nanowire, but at atemperature of at least 50° C. less. In some embodiments the catalyticactivity of the nanowires in an oxidation of CO reaction is the same orbetter than the catalytic activity of a catalyst prepared from bulkmaterial having the same chemical composition as the nanowire, but at atemperature of at least 100° C. less. In some embodiments the catalyticactivity of the nanowires in an oxidation of CO reaction is the same orbetter than the catalytic activity of a catalyst prepared from bulkmaterial having the same chemical composition as the nanowire, but at atemperature of at least 200° C. less.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the selectivity for CO₂ in the oxidation ofCO is greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0times, 3.0 times, or 4.0 times the selectivity for CO₂ compared to thesame reaction under the same conditions but performed with a catalystprepared from bulk material having the same chemical composition as thenanowire. In other embodiments, the selectivity for CO₂ in the oxidationof CO catalyzed by the nanowire is greater than 10%, greater than 20%,greater than 30%, greater than 50%, greater than 75%, or greater than90%.

In one embodiment, the nanowires disclosed herein enable efficientconversion of CO to CO₂ at temperatures less than when the correspondingbulk material is used as a catalyst. For example, in one embodiment, thenanowires enable efficient conversion (i.e., high yield, conversion,and/or selectivity) of CO to CO₂ at temperatures of less than 500° C.,less than 400° C., less than 300° C., less than 200° C., less than 100°C., less than 50° C. or less than 20° C.

Although various reactions have been described in detail, the disclosednanowires are useful as catalysts in a variety of other reactions. Ingeneral, the disclosed nanowires find utility in any reaction utilizinga heterogeneous catalyst and have a catalytic activity such that theyield, conversion, and/or selectivity in reaction catalyzed by thenanowires is better than the yield, conversion and/or selectivity in thesame reaction catalyzed by a corresponding bulk catalyst.

6. Combustion of Hydrocarbons

In another embodiment, the present disclosure provides a nanowire havingcatalytic activity in a reaction for the catalyzed combustion ofhydrocarbons. Such catalytic reactions find utility in catalyticconverters for automobiles, for example by removal of unburnedhydrocarbons in the exhaust by catalytic combustion or oxidation of sootcaptured on catalyzed particle filters resulting in reduction on dieselemissions from the engine. When running “cold”, the exhausts temperatureof a diesel engine is quite low, thus a low temperature catalyst, suchas the disclosed nanowires, is needed to efficiently eliminate allunburned hydrocarbons. In addition, in case of soot removal on catalyzedparticulate filters, intimate contact between the soot and the catalystis require; the open mesh morphology of nanowire catalyst coating isadvandageous to promote such intimate contact between soot and oxidationcatalyst.

In contrast to a corresponding bulk catalyst, Applicants have found thatcertain nanowires, for example the exemplary nanowires disclosed herein,posses a catalytic activity (for example because of their morphology) inthe combustion of hydrocarbons such that the yield, selectivity, and/orconversion is better than when the combustion of hydrocarbons iscatalyzed by a corresponding bulk catalyst. In one embodiment, thedisclosure provides a nanowire having a catalytic activity such that thecombustion of hydrocarbons or soot is greater than at least 1.1 times,1.25 times, 1.50 times, 2.0 times, 3.0 times, or 4.0 times thecombustion of hydrocarbons or soot compared to the same reaction underthe same conditions but performed with a catalyst prepared from bulkmaterial having the same chemical composition as the nanowire. In otherembodiments, the total combustion of hydrocarbons or soot catalyzed bythe nanowire is greater than 10%, greater than 20%, greater than 30%,greater than 50%, greater than 75%, or greater than 90%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the yield of combusted hydrocarbon productsis greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times,3.0 times, or 4.0 times the yield of combusted hydrocarbon productscompared to the same reaction under the same conditions but performedwith a catalyst prepared from bulk material having the same chemicalcomposition as the nanowire. In some embodiments the yield of combustedhydrocarbon products in a reaction catalyzed by the nanowire is greaterthan 10%, greater than 20%, greater than 30%, greater than 50%, greaterthan 75%, or greater than 90%.

The stability of the nanowires is defined as the length of time acatalyst will maintain its catalytic performance without a significantdecrease in performance (e.g., a decrease >20%, >15%, >10%, >5%, orgreater than 1% in hydrocarbon or soot combustion activity). In someembodiments, the nanowires have stability under conditions required forthe hydrocarbon combustion reaction of >1 hr, >5 hrs, >10 hrs, >20hrs, >50 hrs, >80 hrs, >90 hrs, >100 hrs, >150 hrs, >200 hrs, >250hrs, >300 hrs, >350 hrs, >400 hrs, >450 hrs, >500 hrs, >550 hrs, >600hrs, >650 hrs, >700 hrs, >750 hrs, >800 hrs, >850 hrs, >900 hrs, >950hrs, >1,000 hrs, >2,000 hrs, >3,000 hrs, >4,000 hrs, >5,000 hrs, >6,000hrs, >7,000 hrs, >8,000 hrs, >9,000 hrs, >10,000 hrs, >11,000hrs, >12,000 hrs, >13,000 hrs, >14,000 hrs, >15,000 hrs, >16,000hrs, >17,000 hrs, >18,000 hrs, >19,000 hrs, >20,000 hrs, >1 yrs, >2yrs, >3 yrs, >4 yrs or >5 yrs.

In another embodiment, the disclosure provides a nanowire having acatalytic activity in the combustion of hydrocarbons such that thenanowire has the same or better catalytic activity, but at a lowertemperature, compared a catalyst prepared from bulk material having thesame chemical composition as the nanowire. In some embodiments thecatalytic activity of the nanowires in the combustion of hydrocarbons isthe same or better than the catalytic activity of a catalyst preparedfrom bulk material having the same chemical composition as the nanowire,but at a temperature of at least 20° C. less. In some embodiments thecatalytic activity of the nanowires in the combustion of hydrocarbons isthe same or better than the catalytic activity of a catalyst preparedfrom bulk material having the same chemical composition as the nanowire,but at a temperature of at least 50° C. less. In some embodiments thecatalytic activity of the nanowires in the combustion of hydrocarbons isthe same or better than the catalytic activity of a catalyst preparedfrom bulk material having the same chemical composition as the nanowire,but at a temperature of at least 100° C. less. In some embodiments thecatalytic activity of the nanowires in the combustion of hydrocarbons isthe same or better than the catalytic activity of a catalyst preparedfrom bulk material having the same chemical composition as the nanowire,but at a temperature of at least 200° C. less.

7. Evaluation of Catalytic Properties

To evaluate the catalytic properties of the nanowires in a givenreaction, for example those reactions discussed above, various methodscan be employed to collect and process data including measurements ofthe kinetics and amounts of reactants consumed and the products formed.In addition to allowing for the evaluation of the catalyticperformances, the data can also aid in designing large scale reactors,experimentally validating models and optimizing the catalytic process.

One exemplary methodology for collecting and processing data is depictedin FIG. 10. Three main steps are involved. The first step (block 750)comprises the selection of a reaction and catalyst. This influences thechoice of reactor and how it is operated, including batch, flow, etc.(block 754). Thereafter, the data of the reaction are compiled andanalyzed (block 760) to provide insights to the mechanism, rates andprocess optimization of the catalytic reaction. In addition, the dataprovide useful feedbacks for further design modifications of thereaction conditions. Additional methods for evaluating catalyticperformance in the laboratory and industrial settings are described in,for example, Bartholomew, C. H. et al. Fundamentals of IndustrialCatalytic Processes, Wiley-AlChE; 2Ed (1998).

As an example, in a laboratory setting, an Altamira Benchcat 200 can beemployed using a 4 mm ID diameter quartz tube with a 0.5 mm ID capillarydownstream. Quartz tubes with 2 mm or 6 mm ID can also be used.Nanowires are tested in a number of different dilutions and amounts. Insome embodiments, the range of testing is between 10 and 300 mg. In someembodiments, the nanowires are diluted with a non-reactive diluent. Thisdiluent can be quartz (SiO₂) or other inorganic materials, which areknown to be inert in the reaction condition. The purpose of the diluentis to minimize hot spots and provide an appropriate loading into thereactor. In addition, the catalyst can be blended with lesscatalytically active components as described in more detail above.

In a typical procedure, 50 mg is the total charge of nanowire,optionally including diluent. On either side of the nanowires a smallplug of glass wool is loaded to keep the nanowires in place. Athermocouple is placed on the inlet side of the nanowire bed into theglass wool to get the temperature in the reaction zone. Anotherthermocouple can be placed on the downstream end of the nanowire bedinto the catalyst bed itself to measure the exotherms, if any.

When blending the pure nanowire with diluent, the following exemplaryprocedure may be used: x (usually 10-50) mg of the catalyst (either bulkor test nanowire catalyst) is blended with (100-x) mg of diluent.Thereafter, about 2 ml of ethanol or water is added to form a slurrymixture, which is then sonicated for about 10 minutes. The slurry isthen dried in an oven at about 100-140° C. for 2 hours to removesolvent. The resulting solid mixture is then scraped out and loaded intothe reactor between the plugs of quartz wool.

Once loaded into the reactor, the reactor is inserted into the Altamirainstrument and furnace and then a temperature and flow program isstarted. In some embodiment, the total flow is 50 to 100 sccm of gasesbut this can be varied and programmed with time. In one embodiment, thetemperatures range from 450° C. to 900° C. The reactant gases compriseair or oxygen (diluted with nitrogen or argon) and methane in the caseof the OCM reaction and gas mixtures comprising ethane and/or propanewith oxygen for oxidative dehydrogenation (ODH) reactions. Other gasmixtures can be used for other reactions.

The primary analysis of these oxidation catalysis runs is the GasChromatography (GC) analysis of the feed and effluent gases. From theseanalyses, the conversion of the oxygen and alkane feed gases can easilybe attained and estimates of yields and selectivities of the productsand by-products can be determined.

The GC method developed for these experiments employs 4 columns and 2detectors and a complex valve switching system to optimize the analysis.Specifically, a flame ionization detector (FID) is used for the analysisof the hydrocarbons only. It is a highly sensitive detector thatproduces accurate and repeatable analysis of methane, ethane, ethylene,propane, propylene and all other simple alkanes and alkenes up to fivecarbons in length and down to ppm levels.

There are two columns in series to perform this analysis, the first is astripper column (alumina) which traps polar materials (including thewater by-product and any oxygenates generated) until back-flushed laterin the cycle. The second column associated with the FID is a capillaryalumina column known as a PLOT column, which performs the actualseparation of the light hydrocarbons. The water and oxygenates are notanalyzed in this method.

For the analysis of the light non-hydrocarbon gases, a ThermalConductivity Detector (TCD) may be employed which also employees twocolumns to accomplish its analysis. The target molecules for thisanalysis are CO₂, ethylene, ethane, hydrogen, oxygen, nitrogen, methaneand CO. The two columns used here are a porous polymer column known asthe Hayes Sep N, which performs some of the separation for the CO₂,ethylene and ethane. The second column is a molecular sieve column,which uses size differentiation to perform the separation. It isresponsible for the separation of H₂, O₂, N₂, methane and CO.

There is a sophisticated and timing sensitive switching between thesetwo columns in the method. In the first 2 minutes or so, the two columnsare operating in series but at about 2 minutes, the molecular sievecolumn is by-passed and the separation of the first 3 components iscompleted. At about 5-7 minutes, the columns are then placed back inseries and the light gases come off of the sieve according to theirmolecular size.

The end result is an accurate analysis of all of the aforementionedcomponents from these fixed-bed, gas phase reactions. Analysis of otherreactions and gases not specifically described above can be performed ina similar manner.

8. Downstream Products

As noted above, in one embodiment the present disclosure is directed tonanowires useful as catalysts in reactions for the preparation of anumber of valuable hydrocarbon compounds. For example, in one embodimentthe nanowires are useful as catalysts for the preparation of ethylenefrom methane via the OCM reaction. In another embodiment, the nanowiresare useful as catalysts for the preparation of ethylene or propylene viaoxidative dehydrogenation of ethane or propane, respectively. Ethyleneand propylene are valuable compounds, which can be converted into avariety of consumer products. For example, as shown in FIG. 11, ethylenecan be converted into many various compounds including low densitypolyethylene, high density polyethylene, ethylene dichloride, ethyleneoxide, ethylbenzene, linear alcohols, vinyl acetate, alkanes, alphaolefins, various hydrocarbon-based fuels, ethanol and the like. Thesecompounds can then be further processed using methods well known to oneof ordinary skill in the art to obtain other valuable chemicals andconsumer products (e.g. the downstream products shown in FIG. 11).Propylene can be analogously converted into various compounds andconsumer goods including polypropylenes, propylene oxides, propanol, andthe like.

Accordingly, in one embodiment the disclosure provides a method ofpreparing the downstream products of ethylene noted in FIG. 11. Themethod comprises converting ethylene into a downstream product ofethylene, wherein the ethylene has been prepared via a catalyticreaction employing a nanowire, for example any of the nanowiresdisclosed herein. In another embodiment the disclosure provides a methodof preparing low density polyethylene, high density polyethylene,ethylene dichloride, ethylene oxide, ethylbenzene, ethanol or vinylacetate from ethylene, wherein the ethylene has been prepared asdescribed above.

In another embodiment, the disclosure provides a method of preparing aproduct comprising low density polyethylene, high density polyethylene,ethylene dichloride, ethylene oxide, ethylbenzene, ethanol or vinylacetate, alkenes, alkanes, aromatics, alcohols, or mixtures thereof. Themethod comprises converting ethylene into low density polyethylene, highdensity polyethylene, ethylene dichloride, ethylene oxide, ethylbenzene,ethanol or vinyl acetate, wherein the ethylene has been prepared via acatalytic reaction employing a nanowires, for example any of theexemplary nanowires disclosed herein.

In more specific embodiments of any of the above methods, the ethyleneis produced via an OCM or ODH reaction or combinations thereof.

In one particular embodiment, the disclosure provides a method ofpreparing a downstream product of ethylene and/or ethane, wherein thedownstream product is a hydrocarbon fuel. For example, the downstreamproduct of ethylene may be a C₄-C₁₄ hydrocarbon, including alkanes,alkenes and aromatics. Some specific examples include 1-butene,1-hexene, 1-octene, xylenes and the like. The method comprisesconverting methane into ethylene, ethane or combinations thereof by useof a catalytic nanowire, for example any of the catalytic nanowiresdisclosed herein, and further oligomerizing the ethylene and/or ethaneto prepare a downstream product of ethylene and/or ethane. For example,the methane may be converted to ethylene, ethane or combinations thereofvia the OCM reaction as discussed above. The catalytic nanowire may beany nanowire and is not limited with respect to morphology orcomposition. The catalytic nanowire may be an inorganic catalyticpolycrystalline nanowire, the nanowire having a ratio of effectivelength to actual length of less than one and an aspect ratio of greaterthan ten as measured by TEM in bright field mode at 5 keV, wherein thenanowire comprises one or more elements from any of Groups 1 through 7,lanthanides, actinides or combinations thereof. Alternatively, thecatalytic nanowire may be an inorganic nanowire comprising one or moremetal elements from any of Groups 1 through 7, lanthanides, actinides orcombinations thereof and a dopant comprising a metal element, asemi-metal element, a non-metal element or combinations thereof. Thenanowires may additionally comprise any number of doping elements asdiscussed above.

As depicted in FIG. 21, the method begins with charging methane (e.g.,as a component in natural gas) into an OCM reactor. The OCM reaction maythen be performed utilizing a nanowire under any variety of conditions.Water and CO₂ are optionally removed from the effluent and unreactedmethane is recirculated to the OCM reactor.

Ethylene is recovered and charged to an oligomerization reactor.Optionally the ethylene stream may contain CO₂, H₂O, N₂, ethane, C3'sand/or higher hydrocarbons. Oligomerization to higher hydrocarbons(e.g., C₄-C₁₄) then proceeds under any number of conditions known tothose of skill in the art. For example oligomerization may be effectedby use of any number of catalysts known to those skilled in the art.Examples of such catalysts include catalytic zeolites, crystallineborosilicate molecular sieves, homogeneous metal halide catalysts, Crcatalysts with pyrrole ligands or other catalysts. Exemplary methods forthe conversion of ethylene into higher hydrocarbon products aredisclosed in the following references: Catalysis Science & Technology(2011), 1(1), 69-75; Coordination Chemistry Reviews (2011), 255(7-8),861-880; Eur. Pat. Appl. (2011), EP 2287142 A1 20110223; Organometallics(2011), 30(5), 935-941; Designed Monomers and Polymers (2011), 14(1),1-23; Journal of Organometallic Chemistry 689 (2004) 3641-3668;Chemistry—A European Journal (2010), 16(26), 7670-7676; Acc. Chem. Res.2005, 38, 784-793; Journal of Organometallic Chemistry, 695 (10-11):1541-1549 May 15, 2010; Catalysis Today Volume 6, Issue 3, January 1990,Pages 329-349; U.S. Pat. No. 5,968,866; U.S. Pat. No. 6,800,702; U.S.Pat. No. 6,521,806; U.S. Pat. No. 7,829,749; U.S. Pat. No. 7,867,938;U.S. Pat. No. 7,910,670; U.S. Pat. No. 7,414,006 and Chem. Commun.,2002, 858-859, each of which are hereby incorporated in their entiretyby reference.

In certain embodiments, the exemplary OCM and oligomerization modulesdepicted in FIG. 21 may be adapted to be at the site of natural gasproduction, for example a natural gas field. Thus the natural gas can beefficiently converted to more valuable and readily transportablehydrocarbon commodities without the need for transport of the naturalgas to a processing facility.

Referring to FIG. 21, “natural gasoline” refers to a mixture ofoligomerized ethylene products. The mixture may comprise 1-hexene,1-octene, linear, branched or cyclic alkanes of 6 or more hydrocarbons,linear, branched, or cyclic alkenes of 6 or more hydrocarbons,aromatics, such as benzene, toluene, dimethyl benzene, xylenes,napthalene, or other oligomerized ethylene products and combinationsthereof. This mixture finds particular utility in any number ofindustrial applications, for example natural gasoline is used asfeedstock in oil refineries, as fuel blend stock by operators of fuelterminals, as diluents for heavy oils in oil pipelines and otherapplications. Other uses for natural gasoline are well-known to those ofskill in the art.

EXAMPLES Example 1 Pechini Synthesis

Although any metal salt or combination of metal salts can be combinedand processed using the Pechini method to prepare metal oxide catalysts,this example uses Ca, Nd, and Sr salts to prepare a mixed metal oxideOCM catalyst. Equimolar aqueous solutions of strontium nitrate,neodymium nitrate, and calcium nitrate were prepared. Aliquots of eachsolution were mixed together to prepare a desired formulation ofCa_(x)Nd_(y)Sr_(z) where x, y and z each independently represent molefractions of total metal content in moles. Representative examples offormulations include, but are not limited to, Ca₅₀Nd₃₀Sr₂₀,Ca₅₂Nd₄₅Sr₀₅, Ca₇₅Nd₂₂Sr₀₃, and the like. A solution of citric acid wasadded to the metal salt mixture so that the citric acid mole/metal moleratio was 3:1. Ethylene glycol (or any polyfunctional alcohol, forexample glycerol or polyvinyl alcohol) was then added to the citricacid/metal salt solution so that the ethylene glycol/citric acid moleratio was 1:1. The solution was stirred at room temperature for 1 h. Thesolution was placed in a 130° C. oven for 15 h to remove water and topromote resin formation. After 15 h, a hard dark resin was observed. Theresin was placed in furnace and heated to 500° C. for 8 h. The remainingmaterial was then heated to 650° C. for 2 h to yield the desired metaloxide product.

Example 2 Polymer Templated Synthesis

Dextran is a water-soluble polymer with a wide range of molecularweights and is a useful templating source. Briefly, a metal precursorand dextran are dissolved in water to produce a viscous solution. Thesolution is dried to make a metal organic composite and then calcined(oven or microwave) to remove the dextran template. Optionally, multiplemetal precursors are dissolved in a dextran solution. Mixed metal oxidematerials are readily prepared by dissolving different metal salts, inthe desired ratio, in a viscous dextran solution. The solution is driedand calcined as described above to yield mixed metal oxide systems forOCM catalysis. Alternatively, freeze drying may be employed to dry thedextran/metal solution to prepare a more controllable porosity in themetal and mixed metal oxide materials.

Agarose is also used to prepare metal and mixed metal oxides for OCMcatalysts. Agarose readily forms a gel that can be used as templatingsource by impregnating the gel with metal precursors. An agarose gel isimpregnated with a metal precursor. Optionally the wet gel isimpregnated with multiple metal precursors at the same time or step-wisefor the eventual preparation of mixed metal oxide materials.

In an alternative to the above method, the metal-agarose composite istreated with a base to precipitate the metal precursors within the gelframework before calcination. Freeze drying is optionally used to removethe water from the metal-agarose composite. The agarose is removed byoven or microwave calcination to yield metal and mixed metal OCMcatalysts.

Other catalysts are prepared according to the above methods employingany of the polymers and metal compositions disclosed herein.

Example 3 Preparation Mg(OH)₂ Nanowires

FIG. 11 shows a generic reaction scheme for preparing MgO nanowires(with dopant) via a polymer template. The reaction container can beanything from a small vial (for milliliter scale reactions) up to largebottles (for liter reaction scale reactions).

A magnesium solution and a base solution are added to the polymersolution in order to precipitate Mg(OH)₂. The magnesium solution can beof any soluble magnesium salt, e.g. MgX2.6H2O (X═Cl, Br, I), Mg(NO₃)₂,MgSO₄, magnesium acetate, etc. The range of the magnesium concentrationin the reaction mixture is quite narrow, typically at 0.01M. Thecombination of the polymer concentration and the magnesium concentration(i.e. the ratio between the polymer and magnesium ions) can play a partin determining both the nanowires formation process window and theirmorphology.

The base can be any alkali metal hydroxide (e.g. LiOH, NaOH, KOH),soluble alkaline earth metal hydroxide (e.g. Sr(OH)₂, Ba(OH)₂) or anyammonium hydroxide (e.g., NR₄OH, R═H, CH₃, C₂H₅, etc.). Certainselection criteria for the base include: adequate solubility (at leastseveral orders of magnitude higher than Mg(OH)₂ for Mg(OH)₂ nanowires),high enough strength (pH of the reaction mixture should be at least 11)and an inability to coordinate magnesium (for Mg(OH)₂ nanowires) to formsoluble products. LiOH is a preferred choice for Mg(OH)₂ nanowiresformation because lithium may additionally be incorporated in theMg(OH)₂ as a dopant, providing a Li/MgO doped catalyst for OCM.

Another factor concerning the base is the amount of base used or theconcentration ratio of OH⁻/Mg²⁺, i.e. the ratio between the number of OHequivalents added and the number of moles of Mg added. In order to fullyconvert the Mg ions in solution to Mg(OH)₂, the OH/Mg ratio needed is 2.The OH⁻/Mg²⁺ used in the formation of Mg(OH)₂ nanowires ranges from 0.5to 2 and, depending on this ratio, the morphology of the reactionproduct changes from thin nanowires to agglomerations of nanoparticles.The OH⁻/Mg²⁺ ratio is determined by the pH of the reaction mixture,which needs to be at least 11. If the pH is below 11, no precipitationis observed, i.e. no Mg(OH)₂ is formed. If the pH is above 12, themorphology of the nanowires begins to change and more nanoparticles areobtained, i.e. non-selective precipitation.

Considering the narrow window of magnesium concentration in whichMg(OH)₂ nanowires can be obtained, the other key synthetic parametersthat determine the nanowires formation and morphology include but arenot limited to: polymer type and concentration thereof, theconcentration ratio of Mg²⁺/polymer, the concentration ratio ofOH⁻/Mg²⁺, the incubation time of polymer and Mg²⁺; incubation time ofpolymer and the OH⁻; the sequence of adding anion and metal ions; pH;the solution temperature in the incubation step and/or growth step; thetypes of metal precursor salt (e.g., MgCl₂ or Mg(NO₃)₂); the types ofanion precursor (e.g., NaOH or LiOH); the number of additions; the timethat lapses between the additions of the metal salt and anion precursor,including, e.g., simultaneous (zero lapse) or sequential additions.

The Mg salt solution and the base are added sequentially, separated byan incubation time (i.e., the first incubation time). The sequence ofaddition has an effect on the morphology of the nanowires. The firstincubation time can be at least 1 h and it should be longer in the casethe magnesium salt solution is added first. The Mg salt solution and thebase can be added in a single “shot” or in a continuous slow flow usinga syringe pump or in multiple small shots using a liquid dispenserrobot. The reaction is then carried either unstirred or with only mildto moderate stirring for a specific time (i.e., the second incubationtime). The second incubation time is not as strong a factor in thesynthesis of Mg(OH)₂ nanowires, but it should be long enough for thenanowires to precipitate out of the reaction solution (e.g., severalminutes). For practical reasons, the second incubation time can be aslong as several hours. The reaction temperature can be anything fromjust above freezing temperature (e.g., 4° C.) up to 80° C. Thetemperature affects the nanowires morphology.

The precipitated Mg(OH)₂ nanowires are isolated by centrifuging thereaction mixture and decanting the supernatant. The precipitatedmaterial is then washed at least once with a water solution with pH>10to avoid redissolution of the Mg(OH)₂ nanowires. Typically, the washingsolution used can be ammonium hydroxide water solution or an alkalimetal hydroxide solution (e.g., LiOH, NaOH, KOH). This mixture iscentrifuged and the supernatant decanted. Finally, the product can beeither dried (see, Example 5) or resuspended in ethanol for TEManalysis.

FIG. 11 depicts one embodiment for preparing Mg(OH)₂ nanowires. In adifferent embodiment, the order of addition may be reversed, for examplein an exemplary 4 ml scale synthesis of Mg(OH)₂ nanowires and polymerare mixed in a 8 ml vial with 0.02 ml of 1 M LiOH aqueous solution andleft incubating overnight (˜15 h). 0.04 ml of 1 M MgCl₂ aqueous solutionare then added using a pipette and the mixture is mixed by gentleshaking. The reaction mixture is left incubating unstirred for 24 h.After the incubation time, the mixture is centrifuged, and thesupernatant is decanted. The precipitated material is resuspended in 2ml of 0.001 M LiOH aqueous solution (pH=11), the mixture is centrifugedand the supernatant decanted. The obtained Mg(OH)₂ nanowires arecharacterized by TEM as described in Example 4.

Example 4 Characterization of Mg(OH)₂ Nanowires

Mg(OH)₂ nanowires prepared according to Example 3 are characterized byTEM in order to determine their morphology. First, a few microliters(˜500) of ethanol is used to suspend the isolated Mg(OH)₂. The nanowiresare then deposited on a TEM grid (copper grid with a very thin carbonlayer) placed on filter paper to help wick out any extra liquid. Afterallowing the ethanol to dry, the TEM grid is loaded in a TEM andcharacterized. TEM is carried out at 5 KeV in bright field mode in aDeLong LVEM5.

The nanowires are additionally characterized by XRD (for phaseidentification) and TGA (for calcination optimization).

Example 5 Calcination of Mg(OH)₂ Nanowires

The isolated nanowires as prepared in Example 3 are dried in an oven atrelatively low temperature (60-120° C.) prior to calcination.

The dried material is placed in a ceramic boat and calcined in air at450 C.° in order to convert the Mg(OH)₂ nanowires into MgO nanowires.The calcination recipe can be varied considerably. For example, thecalcination can be done relatively quickly like in these two examples:

-   -   load in a muffle oven preheated at 450° C., calcination time=120        min    -   load in a muffle oven (or tube furnace) at room temperature and        ramp to 450° C. with 5° C./min rate, calcination time=60 min

Alternatively, the calcination can be done in steps that are chosenaccording to the TGA signals like in the following example:

-   -   load in a muffle oven (or tube furnace) at room temperature,        ramp to 100° C. with 2° C./min rate, dwell for 60 min, ramp to        280° C. with 2° C./min rate, dwell for 60 min, ramp to 350° C.        with 2° C./min rate, dwell for 60 min and finally ramp to        450° C. with 2° C./min rate, dwell for 60 min.

Generally, a step recipe is preferable since it should allow for abetter, smoother and more complete conversion of Mg(OH)₂ into MgO.Optionally, the calcined product is ground into a fine powder.

Example 6 Preparation of Li Doped MgO Nanowires

Doping of nanowires is achieved by using the incipient wetnessimpregnation method. Before impregnating the MgO nanowires with thedoping solution, the maximum wettability (i.e. the ability of thenanowires to absorb the doping solution before becoming a suspension orbefore “free” liquid is observed) of the nanowires is determined. Thisis a very important step for an accurate absorption of the doping metalon the MgO surface. If too much dopant solution is added and asuspension is formed, a significant amount of dopant will crystallizeunabsorbed upon drying and if not enough dopant solution is added,significant portions of the MgO surface will not be doped.

In order to determine the maximum wettability of the MgO nanowires,small portions of water are dropped on the calcined MgO powder until asuspension is formed, i.e. until “free” liquid is observed. The maximumwettability is determined to be the total amount of water added beforethe suspension forms. The concentration of the doping solution is thencalculated so that the desired amount of dopant is contained in thevolume of doping solution corresponding to the maximum wettability ofthe MgO nanowires. In another way to describe the incipient wetnessimpregnation method, the volume of the doping solution is set to beequal to the pore volume of the nanowires, which can be determined byBET (Brunauer, Emmett, Teller) measurements. The doping solution is thendrawn into the pores by capillary action.

In one embodiment, the doping metal for MgO based catalysts for OCM islithium (see, also, FIG. 11). Thus, in one embodiment the dopant sourcecan be any soluble lithium salt as long as it does not introduceundesired contaminants. Typically, the lithium salts used are LiNO₃,LiOH or Li₂CO₃. LiNO₃ and LiOH are preferred because of their highersolubility. In one embodiment, the lithium content in MgO catalysts forOCM ranges from 0 to 10 wt % (i.e. about 0 to 56 at %).

The calculated amount of dopant solution of the desired concentration isdropped onto the calcined MgO nanowires. The obtained wet powder isdried in an oven at relatively low temperature (60-120° C.) and calcinedusing one of the recipes described above. It is noted that, during thisstep, no phase transition occurs (MgO has already been formed in theprevious calcination step) and thus a step recipe (see previousparagraph) may not be necessary.

The dopant impregnation step can also be done prior to the calcination,after drying the Mg(OH)₂ nanowires isolated from the reaction mixture.In this case, the catalyst can be calcined immediately after the dopantimpregnation, i.e. no drying and second calcination steps would berequired since its goals are accomplished during the calcination step.

Three identical syntheses are made in parallel. In each synthesis, 80 mlof concentrated polymer solution is mixed in a 100 ml glass bottle with0.4 ml of 1 M LiOH aqueous solution and left incubating for 1 h. 0.8 mlof 1 M MgCl₂ aqueous solution are added using a pipette and the mixtureis mixed by gently shaking it. The reaction mixture is left incubatingunstirred for 72 h at 60° C. in an oven. After the incubation time, themixture is centrifuged. The precipitated material is resuspended in 20ml of 0.06 M NH₄OH aqueous solution (pH=11), the mixture is centrifugedand the supernatant decanted. The obtained Mg(OH)₂ nanowires areresuspended in ethanol. The ethanol suspensions of the three identicalsyntheses are combined and a few microliters of the ethanol suspensionare used for TEM analysis. The ethanol suspension is centrifuged and thesupernatant decanted. The gel-like product is transferred in a ceramicboat and dried for 1 h at 120° C. in a vacuum oven.

The dried product is calcined in a tube furnace using a step recipe(load in the furnace at room temperature, ramp to 100° C. with 2° C./minrate, dwell for 60 min, ramp to 280° C. with 2° C./min rate, dwell for60 min, ramp to 350° C. with 2° C./min rate, dwell for 60 min, ramp to450° C. with 2° C./min rate, dwell for 60 min and finally cool to roomtemperature). The calcined product is ground to a fine powder.

10 mg of the calcined product are impregnated with a LiOH aqueoussolution. First, the maximum wettability is determined by adding waterto the calcined product in a ceramic boat until the powder is saturatedbut no “free” liquid was observed. The maximum expected wettability isabout 12 μl. Since the target doping level is 1 wt % lithium, thenecessary concentration of the LiOH aqueous solution is calculated to be1.2 M. The calcined product is dried again for 1 h at 120° C. to removethe water used to determine the wettability of the powder. 12 μl of the1.2 M LiOH solution are dropped on the MgO nanowires powder. The wetpowder is dried for 1 h at 120° C. in a vacuum oven and finally calcinedin a muffle oven (load at room temperature, ramp to 460° C. with 2°C./min ramp, dwell for 120 min).

Example 7 OCM Catalyzed by La₂O₃ Nanowires

A 20 mg sample of a polymer-based Sr (5%) doped La₂O₃ catalyst isdiluted with 80 mg of quartz sand and placed into a reactor (run WPS21).The gas flows are held constant at 9 sccm methane, 3 sccm oxygen and 6sccm of argon. The upstream temperature (just above the bed) is variedfrom 500° C. to 800° C. in 100° C. increments and then decreased backdown to 600° C. in 50° C. increments. The vent gas analysis is gatheredat each temperature level.

The polymer-based nanowires according to the present disclosure areexpected to comprise better OCM activity (i.e., conversion of methane,C2 selectivity, yield, etc.) compared to a corresponding bulk catalyst.

Example 8 Oxidative Dehydrogenation Catalyzed by MgO Nanowires

A 10 mg sample of polymer-based Li doped MgO catalyst is diluted with 90mg of quartz sand and placed in a reactor. The gas flows are heldconstant at 8 sccm alkane mix, 2 sccm oxygen and 10 sccm of argon. Theupstream temperature (just above the bed) is varied from 500° C. to 750°C. in 50-100° C. increments. The vent gas analysis is gathered at eachtemperature level.

The polymer-based nanowires according to the present disclosure areexpected to comprise better conversion of ethane and propane compared toa corresponding bulk catalyst.

Example 9 Preparation of Sr Doped La₂O₃ Nanowires

Sr doped La₂O₃ nanowires are prepared according to the following method.

A 57 mg aliquot of La₂O₃ nanowires prepared as described herein is thenmixed with 0.174 ml of a 0.1 M solution of Sr(NO₃)₂. This mixture isthen stirred on a hot plate at 90° C. until a paste was formed.

The paste is then dried for 1 h at 120° C. in a vacuum oven and finallycalcined in a muffle oven in air according to the following procedure:(1) load in the furnace at room temperature; (2) ramp to 200° C. with 3°C./min rate; (3) dwell for 120 min; (3) ramp to 400° C. with 3° C./minrate; (4) dwell for 120 min; (5) ramp to 500° C. with 3° C./min rate;and (6) dwell for 120 min. The calcined product is then ground to a finepowder.

Example 10 Preparation of La₂O₃ Nanowires

Two identical syntheses are made in parallel. In each synthesis, 360 mlof polymer solution are mixed in a 500 ml plastic bottle with 1.6 ml of0.1 M LaCl₃ aqueous solution and left incubating for at least 1 hour.After this incubation period, a slow multistep addition is conductedwith 20 ml of 0.1 M LaCl3 solution and 40 ml of 0.3 M NH4OH. Thisaddition is conducted in 24 hours and 100 steps. The reaction mixture isleft stirred for at least another hour at room temperature. After thattime the suspension is centrifuged in order to separate the solid phasefrom the liquid phase. The precipitated material is then re-suspended in25 ml of ethanol. The ethanol suspensions from the two identicalsyntheses are combined and centrifuged in order to remove un-reactedspecies. The gel-like product remaining is then dried for 15 hours at65° C. in an oven and then calcined in a muffle oven in air (load in thefurnace at room temperature, ramp to 100° C. with 2° C./min rate, dwellfor 30 min, ramp to 400° C. with 2° C./min rate, dwell for 240 min, rampto 550° C. with 2° C./min rate, dwell for 240 min, cool to roomtemperature).

Example 11 Preparation of Mg/Na Doped La₂O₃ Nanowires

Two identical syntheses are made in parallel. In each synthesis, 360 mlof polymer solution are mixed in a 500 ml plastic bottle with 1.6 ml of0.1 M LaCl₃ aqueous solution and left incubating for at least 1 hour.After this incubation period, a slow multistep addition is conductedwith 20 ml of 0.1 M LaCl₃ solution and 40 ml of 0.3 M NH₄OH. Thisaddition is conducted in 24 hours and 100 steps. The reaction mixture isleft stirred for at least another hour at room temperature. After thattime, the suspension is centrifuged in order to separate the solid phasefrom the liquid phase. The precipitated material is then resuspended in25 ml of ethanol. The ethanol suspensions from the two identicalsyntheses are combined and centrifuged in order to remove un-reactedspecies. The gel-like product remaining is then dried for 15 hours at65° C. in an oven.

The target doping level is 20 at % Mg and 5 at % Na at % refers toatomic percent). 182 mg of the dried product are suspended in 2.16 mldeionized water, 0.19 ml 1 M Mg(NO₃)₂ aqueous solution and 0.05 ml 1MNaNO₃ aqueous solution. The resulting slurry is stirred at roomtemperature for 1 hour, sonicated for 5 min, then dried at 120° C. inand oven until the powder is fully dried and finally calcined in amuffle oven in air (load in the furnace at room temperature, ramp to100° C. with 2° C./min rate, dwell for 30 min, ramp to 400° C. with 2°C./min rate, dwell for 60 min, ramp to 550° C. with 2° C./min rate,dwell for 60 min, ramp to 650° C. with 2° C./min rate, dwell for 60 min,ramp to 750° C. with 2° C./min rate, dwell for 240 min, cool to roomtemperature).

Example 12 Oxidative Coupling of Methane Catalyzed by Mg/Na Doped La₂O₃Nanowires

50 mg of Mg/Na-doped La₂O₃ nanowires catalyst from example 12 are placedinto a reactor tube (4 mm ID diameter quartz tube with a 0.5 mm IDcapillary downstream), which is then tested in an Altamira Benchcat 203.The gas flows are held constant at 46 sccm methane and 54 sccm air,which correspond to a CH₄/O₂ ratio of 4 and a feed gas-hour spacevelocity (GHSV) of about 130000/hour. The reactor temperature is variedfrom 400° C. to 450° C. in a 50° C. increment, from 450° C. to 550° C.in 25° C. increments and from 550° C. to 750° C. in 50° C. increments.The vent gases are analyzed with gas chromatography (GC) at eachtemperature level.

In another example, 50 mg of Mg/Na-doped La₂O₃ nanowires catalyst fromexample 12 are placed into a reactor tube (4 mm ID diameter quartz tubewith a 0.5 mm ID capillary downstream), which is then tested in anAltamira Benchcat 203. The gas flows are held constant at 46 sccmmethane and 54 sccm air, which correspond to a feed gas-hour spacevelocity (GHSV) of about 130000 h⁻¹. The CH4/O2 ratio is 5.5. Thereactor temperature is varied from 400° C. to 450° C. in a 50° C.increment, from 450° C. to 550° C. in a 25° C. increments and from 550°C. to 750° C. in 50° C. increments. The vent gases are analyzed with gaschromatography (GC) at each temperature level.

Example 13 Nanowire Synthesis

Nanowires may be prepared by hydrothermal synthesis from metal hydroxidegels (made from metal salt+base). In some embodiments, this method isapplicable to lanthanides, for example La, Nd, Pr, Sm, Eu, andlanthanide containing mixed oxides.

Alternatively, nanowires can be prepared by synthesis from metalhydroxide gel (made from metal salt+base) under reflux conditions. Insome embodiments, this method is applicable to lanthanides, for exampleLa, Nd, Pr, Sm, Eu, and lanthanide containing mixed oxides.

Alternatively, the gel can be aged at room temperature. Certainembodiments of this method are applicable for making magnesiumhydroxychloride nanowires, which can be converted to magnesium hydroxidenanowires and eventually to MgO nanowires. In a related method,hydrothermal treatment of the gel instead of aging is used.

Nanowires may also be prepared by polyethyleneglycol assistedhydrothermal synthesis. For example, Mn containing nanowires may beprepared according to this method using methods known to those skilledin the art. Alternatively, hydrothermal synthesis directly from theoxide can be used.

Example 14 Preparation of Nd₂O₃, Eu₂O₃ and Pr₂O₃ Nanowires

Three syntheses are made in parallel. In each synthesis, 10 ml ofpolymer solution are mixed in a 60 ml glass vial with 25 μl of 0.08MNdCl₃, EuCl₃ or PrCl₃ aqueous solutions, respectively and leftincubating for at least 1 hour. After this incubation period, a slowmultistep addition is conducted with 630 μl of 0.08M LaCl₃, EuCl₃ orPrCl₃ aqueous solutions, respectively and 500 μl of 0.3M NH4OH. Thisaddition is conducted in 33 hours and 60 steps. The reaction mixturesare left stirred for at least another 10 hour at room temperature. Afterthat time the suspensions are centrifuged in order to separate the solidphase from the liquid phase. The precipitated material is thenre-suspended in 4 ml of ethanol. The ethanol suspensions are centrifugedin order to finish removing un-reacted species. The gel-like productremaining is then dried for 1 hours at 65° C. in an oven and thencalcined in a muffle oven in air (load in the furnace at roomtemperature, ramp to 100° C. with 2° C./min rate, dwell for 30 min, rampto 500° C. with 2° C./min rate, dwell for 240 min, cool to roomtemperature). The obtained Nd(OH)₃, Eu(OH)₃ and Pr(OH)₃ nanowires werecharacterized by TEM before being dried.

Example 15 Preparation of Ce₂O₃/La₂O₃ Mixed Oxide Nanowires

In this synthesis, 15 ml of polymer are mixed in a 60 ml glass vial with15 μl of 0.1 M La(NO₃)₃ aqueous solution and left incubating for about16 hour. After this incubation period, a slow multistep addition isconducted with 550 μl of 0.2M Ce(NO₃)₃ aqueous solution, 950 μl of 0.2MLa(NO₃)₃ aqueous solution and 1500 μl of 0.4M NH₄OH. This addition isconducted in 39 hours and 60 steps. The reaction mixtures are leftstirred for at least another 10 hours at room temperature. After thattime the suspensions are centrifuged in order to separate the solidphase from the liquid phase. The precipitated material is thenre-suspended in 4 ml of ethanol. The ethanol suspensions are centrifugedin order to finish removing un-reacted species. The gel-like productremaining is then dried for 1 hours at 65° C. in an oven and thencalcined in a muffle oven in air (load in the furnace at roomtemperature, ramp to 100° C. with 2° C./min rate, dwell for 30 min, rampto 500° C. with 2° C./min rate, dwell for 120 min, cool to roomtemperature).

Example 16 Oligomerization of Ethylene to Liquid Hydrocarbon Fuels withHigh Aromatics Content

0.1 g of the zeolite ZSM-5 is loaded into a fixed bed micro-reactor andheated at 400° C. for 2 h under nitrogen to activate the catalyst. TheOCM effluent, containing ethylene and ethane, is reacted over thecatalyst at 400° C. at a flow rate of 50 mL/min and GSHV=3000−10000mL/(g h). The reaction products are separated into liquid and gascomponents using a cold trap. The gas and liquid components are analyzedby gas chromatography. C5-C10 hydrocarbon liquid fractions, such asxylene and isomers thereof, represent ≧90% of the liquid product ratiowhile the C11-C15 hydrocarbon fraction represents the remaining 10% ofthe product ratio.

Example 17 Oligomerization of Ethylene to Liquid Hydrocarbon Fuels withHigh Olefins Content

0.1 g of the zeolite ZSM-5 doped with nickel is loaded into a fixed bedmicro-reactor and heated at 350° C. for 2 h under nitrogen to activatethe catalyst. The OCM effluent, containing ethylene and ethane, isreacted over the catalyst at 250−400° C. temperature rage withGSHV=1000−10000 mL/(g h). The reaction products are separated intoliquid and gas components using a cold trap. The gas and liquidcomponents are analyzed by gas chromatography. C₄-C₁₀ olefin hydrocarbonliquid fractions, such as butene, hexane and octene represent ≧95% ofthe liquid product ratio while the C₁₂-C₁₈ hydrocarbon fractionrepresents the remaining 5% of the product ratio. Some trace amounts ofodd numbered olefins are also possible in the product.

Example 18 OCM Catalyzed by La₂O₃ Nanowires

50 mg of a nanowire catalyst as described herein are placed into areactor tube (4 mm ID diameter quartz tube with a 0.5 mm ID capillarydownstream), which is then tested in an Altamira Benchcat 203. The gasflows are held constant at 46 sccm methane and 54 sccm air, whichcorrespond to a CH₄/O2 ratio of 4 and a feed gas-hour space velocity(GHSV) of about 130000/hour. The reactor temperature is varied from 400°C. to 500° C. in a 100° C. increment and from 500° C. to 850° C. in 50°C. increments. The vent gases are analyzed with gas chromatography (GC)at each temperature level.

Example 19 Preparation of Catalytic Material Comprising CordieriteHoneycomb Ceramic Supported Nd₂O₃ Nanowires

Nd₂O₃ nanowires are prepared in a manner analogous to those describedherein.

A 400 mg aliquot of Nd₂O₃ nanowires is mixed with 2 g of DI water andplaced into a 5 ml glass vial containing 2 mm Yttria Stabilized Zirconiamilling balls. The vial is placed on a shaker at 2000 RPM and agitatedfor 30 minutes. A thick slurry is obtained.

A ⅜ inch diameter core is cut along the channel direction into a 400CPSI (channel per square inche) cordierite honeycomb monolith and cut inlength so the core volume is approximately 1 ml.

The core is placed into a ⅜ inch tube, and the catalyst slurry is fed ontop of the ceramic core and pushed with compressed air through themonolith channel. The excess slurry is captured into a 20 ml vial. Thecoated core is removed from the ⅜ inch tube and placed into a dryingoven at 200° C. for 1 hour.

The coating step is repeated twice more time with the remaining slurryfollowed by drying at 200° C. and calcination at 500° C. for 4 hours.The catalyst amount deposited on the monolith channel walls isapproximately 50 mg and comprises very good adhesion to the ceramicwall.

Example 20 Preparation of Catalytic Material Comprising Silicon CarbideCeramic Foam Supported Nd₂O₃ Nanowires

Nd₂O₃ nanowires are prepared in a manner analogous to the aboveexamples.

A 400 mg aliquot of Nd₂O₃ nanowires is mixed with 2 g of DI water andplaced into a 5 ml glass vial containing 2 mm Yttria Stabilized Zirconiamilling balls. The vial is placed on a shaker at 2000 RPM and agitatedfor 30 minutes. A thick slurry is obtained.

A ⅜ inch diameter core is cut from a 65 PPI (Pore Per Inch) SiC foam andcut in length so the core volume is approximately 1 ml.

The core is placed into a ⅜ inch tube and the catalyst slurry is fed ontop of the ceramic core and pushed with compressed air through themonolith channel. The excess slurry is captured into a 20 ml vial. Thecoated core is removed from the ⅜ inch tube and placed into a dryingoven at 200° C. for 1 hour.

The coating step is repeated twice more time with the remaining slurryfollowed by drying at 200° C. and calcination at 500° C. for 4 hours.The catalyst amount deposited on the monolith channel walls isapproximately 60 mg and comprises very good adhesion to the ceramicmesh.

Example 21 Preparation of Catalytic Material Comprising Silicon Carbideand Nd₂O₃ Nanowires

Nd₂O₃ nanowires are prepared in a manner analogous to the above examples

A 400 mg aliquot of Nd₂O₃ nanowires is dry blend mixed with 400 mg of200-250 mesh SiC particles for 10 minutes or until the mixture appearshomogeneous and wire clusters are no longer visible. The mixture is thenplaced into a ¼ inch die and pressed in 200 mg batches. The pressedpellets are then placed into an oven and calcined at 600° C. for 2hours. The crush strength of the pellet obtained is comparable to thecrush strength of a pellet made with only Nd₂O₃ nanowires.

Example 22 Preparation of Sr Doped La₂O₃ Nanowires

Sr doped La₂O₃ nanowires are prepared according to the following method.

A 57 mg aliquot of La₂O₃ nanowires prepared as described herein is thenmixed with 0.174 ml of a 0.1 M solution of Sr(NO₃)₂. This mixture isthen stirred on a hot plate at 90° C. until a paste was formed.

The paste is then dried for 1 h at 120° C. in a vacuum oven and finallycalcined in a muffle oven in air according to the following procedure:(1) load in the furnace at room temperature; (2) ramp to 200° C. with 3°C./min rate; (3) dwell for 120 min; (3) ramp to 400° C. with 3° C./minrate; (4) dwell for 120 min; (5) ramp to 500° C. with 3° C./min rate;and (6) dwell for 120 min. The calcined product is then ground to a finepowder.

The various embodiments described above can be combined to providefurther embodiments. All of the U.S. patents, U.S. patent applicationpublications, U.S. patent applications, foreign patents, foreign patentapplications and non-patent publications referred to in thisspecification and/or listed in the Application Data Sheet, areincorporated herein by reference, in their entirety. Aspects of theembodiments can be modified, if necessary to employ concepts of thevarious patents, applications and publications to provide yet furtherembodiments. These and other changes can be made to the embodiments inlight of the above-detailed description. In general, in the followingclaims, the terms used should not be construed to limit the claims tothe specific embodiments disclosed in the specification and the claims,but should be construed to include all possible embodiments along withthe full scope of equivalents to which such claims are entitled.Accordingly, the claims are not limited by the disclosure.

1. A method for preparing a nanowire comprising a metal oxide, a metaloxy-hydroxide, a metal oxycarbonate or a metal carbonate, the methodcomprising: a) providing a solution comprising a plurality of polymertemplates; (b) introducing at least one metal ion and at least one anionto the solution under conditions and for a time sufficient to allow fornucleation and growth of a nanowire comprising a plurality of metalsalts (M_(m)X_(n)Z_(p)) on the template; and (c) optionally convertingthe nanowire (M_(m)X_(n)Z_(p)) to a metal oxide nanowire comprising aplurality of metal oxides (M_(x)O_(y)), metal oxy-hydroxides(M_(x)O_(y)OH_(z)), metal oxycarbonates (M_(x)O_(y)(CO₃)_(z)), metalcarbonate (M_(x)(CO₃)_(y)) or combinations thereof wherein: M is, ateach occurrence, independently a metal element from any of Groups 1through 7, lanthanides or actinides; X is, at each occurrence,independently hydroxide, carbonate, bicarbonate, phosphate,hydrogenphosphate, dihydrogenphosphate, sulfate, nitrate or oxalate; Zis O; n, m, x and y are each independently a number from 1 to 100; and pis a number from 0 to
 100. 2. The method of claim 1, wherein the polymertemplate comprises PVP (polyvinlpyrrolidone), PVA (polyvinylalcohol),PEI (polyethyleneimine), PEG (polyethyleneglycol), polyethers,polyesters, polyamides, dextran, sugar polymers, functionalizedhydrocarbon polymers, functionalized polystyrene, polylactic acid,polycaprolactone, polyglycolic acid, poly(ethylene glycol)-polypropyleneglycol)-poly(ethylene glycol) or copolymers or combinations thereof. 3.The method of claim 1, further comprising freeze drying the nanowire. 4.The method of claim 1, wherein the solution comprising the polymertemplate is in the form of a gel.
 5. The method of claim 4, furthercomprising a step of base treatment and precipitating at least onemetal.
 6. The method of claim 1, further comprising use of two or moredifferent metal ions.
 7. A method for preparing a nanowire comprising ametal oxide, a metal oxy-hydroxide, a metal oxycarbonate or a metalcarbonate, the method comprises: a) providing a solution comprising aplurality of a multifunctional coordinating ligands; (b) introducing atleast one metal ion to the solution, thereby forming a metal ion-ligandcomplex; and (c) introducing a polyalcohol to the solution, wherein thepolyalcohol polymerizes with the metal-ion ligand complex to form apolymerized metal ion-ligand complex.
 8. The method of claim 7, whereinthe multifunctional coordinating ligand is an alpha-hydroxycarboxylicacid.
 9. The method of claim 8, wherein the multifunctional coordinatingligand is citric acid.
 10. The method of claim 7, wherein thepolyalcohol is ethylene glycol or glycerol.
 11. The method of claim 7further comprising heating the polymerized metal ion-ligand complex toremove substantially all organic material.
 12. The method of claim 7further comprising heating the polymerized metal ion-ligand complex toobtain a metal oxide.
 13. A method for preparing metal oxide, metaloxy-hydroxide, metal oxycarbonate or metal carbonate catalytic nanowiresin a core/shell structure, the method comprising: (a) providing asolution that includes a plurality of polymer templates; (b) introducinga first metal ion and a first anion to the solution under conditions andfor a time sufficient to allow for nucleation and growth of a firstnanowire (M1_(m1)X1_(n1)Z_(p1)) on the template; and (c) introducing asecond metal ion and optionally a second anion to the solution underconditions and for a time sufficient to allow for nucleation and growthof a second nanowire (M2_(m2)X2_(n2)Z_(p2)) on the first nanowire(M1_(m1)X1_(n1)Z_(p1)); (d) converting the first nanowire(M1_(m1)X1_(n1)Z_(p1)) and the second nanowire (M2_(m2)X2_(n2)Z_(p2)) tothe respective metal oxide nanowires (M1_(x1)O_(y1)) and(M2_(x2)O_(y2)), the respective metal oxy-hydroxide nanowires(M1_(x1)O_(y1)OH_(z1)) and (M2_(x2)O_(y2)OH_(z2)) the respective metaloxycarbonate nanowires (M1_(x1)O_(y1)(CO₃)_(z1)) and(M2_(x2)O_(y2)(CO₃)_(z2)) or the respective metal carbonate nanowires(M1_(x1)(CO₃)_(y1)) and (M2_(x2)(CO₃)_(y2)), wherein: M1 and M2 are thesame or different and independently selected from a metal element; X1and X2 are the same or different and independently hydroxide, carbonate,bicarbonate, phosphate, hydrogenphosphate, dihydrogenphosphate, sulfate,nitrate or oxalate; Z is O; n1, m1n2, m2, x1, y1, z1, x2, y2 and z2 areeach independently a number from 1 to 100; and p1 and p2 areindependently a number from 0 to
 100. 14. The method of claim 13,wherein the polymer template comprises PVP (polyvinlpyrrolidone), PVA(polyvinylalcohol), PEI (polyethyleneimine), PEG (polyethyleneglycol),polyethers, polyesters, polyamides, dextran, sugar polymers,functionalized hydrocarbon polymers, functionalized polystyrene,polylactic acid, polycaprolactone, polyglycolic acid, poly(ethyleneglycol)-poly(propylene glycol)-poly(ethylene glycol) or copolymers orcombinations thereof.
 15. The method of claim 13, wherein M1 and M2 aredifferent.
 16. A method for preparing a catalytic nanowire, the methodcomprising: admixing (A) with a mixture comprising (B) and (C); admixing(B) with a mixture comprising (A) and (C); or admixing (C) with amixture comprising (A) and (B) to obtain a mixture comprising (A), (B)and (C), wherein (A), (B), and (C) comprise, respectively: (A) a polymertemplate; (B) one or more salts comprising one or more elements selectedfrom Groups 1 through 7, lanthanides and actinides and hydrates thereof;and (C) one or more anion precursors.
 17. The method of claim 16,wherein the mixture comprising (B) and (C) has been prepared by admixing(B) and (C), the mixture comprising (A) and (C) has been prepared byadmixing (A) and (C) or the mixture comprising (A) and (B) has beenprepared by admixing (A) and (B).
 18. The method of claim 16, whereinthe one or more salts comprise chlorides, bromides, iodides, nitrates,sulfates, acetates, oxides, oxalates, oxyhalides, oxynitrates,phosphates, hydrogenphosphate, dihydrogenphosphate or mixtures thereof.19. The method of claim 16, wherein the one or more salts compriseMgCl₂, LaCl₃, ZrCl₄, WCl₄, MoCl₄, MnCl₂MnCl₃, Mg(NO₃)₂, La(NO₃)₃,ZrOCl₂, Mn(NO₃)₂, Mn(NO₃)₃, ZrO(NO₃)₂, Zr(NO₃)₄ or mixtures thereof. 20.The method of claim 16, wherein the one or more salts comprise Mg, Ca,Mg, W, La, Nd, Sm, Eu, W, Mn, Zr or mixtures thereof.
 21. The method ofclaim 16, wherein the one or more anion precursors comprises alkalimetal hydroxides, alkaline earth metal hydroxides, carbonates,bicarbonates, ammonium hydroxides, or mixtures thereof.
 22. The methodof claim 21, wherein the one or more anion precursors comprises LiOH,NaOH, KOH, Sr(OH)₂, Ba(OH)₂, Na₂CO₃, K₂CO₃, NaHCO₃, KHCO₃, and NR₄OH,wherein R is selected from H, and C₁-C₆ alkyl.
 23. The method of claim16, wherein the polymer template comprises PVP (polyvinlpyrrolidone),PVA (polyvinylalcohol), PEI (polyethyleneimine), PEG(polyethyleneglycol), polyethers, polyesters, polyamides, dextran, sugarpolymers, functionalized hydrocarbon polymers, functionalizedpolystyrene, polylactic acid, polycaprolactone, polyglycolic acid,poly(ethylene glycol)-polypropylene glycol)-poly(ethylene glycol) orcopolymers or combinations thereof.
 24. The method of claim 16, furthercomprising allowing the mixture comprising (A), (B), and (C) to stand ata temperature of from about 4° C. to about 80° C. for a period of timesufficient to allow nucleation of the catalytic nanowires
 25. The methodof claim 16, further comprising adding a doping element comprising metalelements, semi-metal elements, non-metal elements or combinationsthereof to the mixture comprising (A), (B), and (C).
 26. The method ofclaim 16, further comprising calcining the nanowires.
 27. The method ofclaim 26, wherein calcining the nanowires comprises heating thenanowires at 450° C. or greater for at least 60 min.
 28. The method ofclaim 16, further comprising doping the nanowires, wherein doping thenanowires comprises contacting the nanowires with a solution comprisinga dopant and evaporating any excess liquid, wherein the dopant comprisesa metal element, a semi-metal element, a non-metal element orcombinations thereof.
 29. A method for preparing metal oxide nanowires,the method comprising: (a) providing a solution comprising a pluralityof polymer templates; and (b) introducing a compound comprising a metalto the solution under conditions and for a time sufficient to allow fornucleation and growth of a nanowire (M_(m)Y_(n)) on the template;wherein: M is a metal element from any of Groups 1 through 7,lanthanides or actinides; Y is O, n and m are each independently anumber from 1 to
 100. 30. The method of claim 29, wherein the polymertemplate comprises PVP (polyvinlpyrrolidone), PVA (polyvinylalcohol),PEI (polyethyleneimine), PEG (polyethyleneglycol), polyethers,polyesters, polyamides, dextran, sugar polymers, functionalizedhydrocarbon polymers, functionalized polystyrene, polylactic acid,polycaprolactone, polyglycolic acid, poly(ethyleneglycol)-poly(propylene glycol)-poly(ethylene glycol) or copolymers orcombinations thereof.
 31. A nanowire prepared according to the method ofclaim
 1. 32. A catalytic material comprising the nanowire of claim 31.33. A method for the preparation of a downstream product of ethylene,the method comprising converting methane into ethylene in the presenceof the nanowire of claim 31 and further oligomerizing the ethylene toprepare a downstream product of ethylene.
 34. A process for thepreparation of ethylene from methane comprising contacting a mixturecomprising oxygen and methane at a temperature below 900° C. with thenanowire of claim
 31. 35. The method of any of claim 16, wherein thepolymer template is functionalized with at least one of amine,carboxylic acid, sulfate, alcohol or thiol groups.
 36. The method ofclaim 35, wherein the polymer template comprises a hydrocarbon polymeror a polystyrene polymer.